Synthesis and optical properties of pencil-like and shuttle-like ZnO microrods

The pencil-like and shuttle-like ZnO microrods have been fabricated on Si (100) substrates by chemical vapor deposition. Structure characterization results show that the microrods are perfect single crystals with the wurtzite structure along the [0001] growth direction and have diameters ranging from 100 nm to 2 μm and lengths up to 10 μm. Room-temperature photoluminescence measurements of ZnO microstructures exhibit an intensive ultraviolet peak at 390 nm and a broad peak centered at about 526 nm, which can be attributed to the free exciton emission and the deep level emission, respectively. Cathodoluminescence measurements show the same ultraviolet and green emissions as seen in the photoluminescence results. A possible growth mechanism of ZnO microrods is finally proposed.     

高质量ZnO微米棒的制备及其光学性质

利用水热法制备ZnO微米棒。醋酸镁[Mg(CH3COO)2.4H2O]、醋酸锌[Zn(CH3COO)2.2H2O]和六次甲基四胺(C6H12N4)以一定比例配置成反应溶液,把反应溶液加热到90℃,反应时间为24h,能够在硅衬底上生长高质量的ZnO微米棒。用扫描电镜(SEM)和X射线衍射仪对ZnO微米棒的晶体结构和表面形貌进行了分析,结果表明,样品为细长条棒状结构,呈现六方纤锌矿结构,长径比可达10∶1,并且在[002]方向择优生长。在样品中并未发现镁离子,它有可能扮演着催化剂的角色。对ZnO微米棒的光致发光性能进行测量,由PL光谱分析可知,样品在384nm处有一个紫外发光峰,半峰全宽为13nm,紫外发光峰强度比可见发光峰强度大的多,样品的质量较好。     

Excitation wavelength dependent photoluminescence intensity of six faceted prismatic ZnO microrods

This article presents the investigation on the large-scale synthesis of ZnO microrods with a simple low temperature hydrothermal method without using surfactants, organic solvents, or catalytic reagents. The synthesized ZnO powder is characterized with different techniques. The X-ray diffraction study reveals the excellent crystal quality of the ZnO product possessing the hexagonal (wurtzite-type) crystal structure. The scanning electron microscope observation confirms the formation of six faceted prismatic hexagonal ZnO microrods with the aspect ratio of 10. It also reveals that the ZnO microrods grow along the (0 0 0 1) direction and finally emerge with a sharp tip because of the existence of polar faces. The UV–vis spectrum shows a sharp absorption peak centered at 370 nm, which is in a good agreement with the equivalent bulk band gap value. The strong UV absorption peak implies the excellent crystal quality of the synthesized ZnO microrods. Room temperature photoluminescence spectroscopic study of the ZnO microrods with different excitation wavelengths reveals a strong band edge emission peak centered at 398 nm and a defect related visible blue emission peak at 460 nm. The decrease in photoluminescence intensity with negligible red shift in peak position is observed with increasing excitation wavelength.     

Influence of Sb on a controlled-growth of aligned ZnO nanowires in nanoparticle-assisted pulsed-laser deposition

Single-crystalline ZnO nanowires on a sapphire substrate have been synthesized by a nanoparticle-assisted pulsed-laser deposition (NAPLD) using a pure and Sb₂O₃ doped ZnO target. Low density and vertically well-aligned ZnO nanowires were grown on hexagonal cone-shape ZnO cores by introduction of a ZnO buffer layer. More than 90% of the ZnO cores of the Sb-induced ZnO nanowires are formed in the same size of 400 nm. The ZnO nanowires consist of single-crystalline wurtzite ZnO crystal and grow along [0001] direction. The room-temperature photoluminescence spectrum exhibited a strong ultraviolet emission at around 380 nm and a relatively low broad band emission in the visible region, indicating a low concentration of structural defect in the nanowires. Sb can be used as one of the effective additives to control the morphology and alignment of ZnO nanowires synthesized by NAPLD.     

Structural and optical properties of ZnO and Al-doped ZnO microrods obtained by spray pyrolysis method using different solvents

ZnO and Al-doped ZnO microrods were obtained by spray pyrolysis method using different solvents such as methanol and propanol. The effect of the type of solvent in the starting solution on the structural, morphological and optical properties of the samples was investigated. X-ray diffraction patterns showed that the undoped and Al-doped ZnO microrods exhibited hexagonal crystal structure with a preferred orientation along (0 0 2) direction. Surface morphology of the samples obtained by scanning electron microscopy revealed that undoped and Al-doped ZnO microrods grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm irrespective of solvents used. Optical studies indicated that microrods had a low transmittance (≅30%) and the band gap increased from 3.24 to 3.26 eV upon Al doping. Photoluminescence measurements indicated the existence of two emission bands in the spectra: one sharp ultraviolet luminescence at ∼383 nm and one broad visible emission ranging from 420 to 580 nm.     

ZnO Nanorods Produced by the Method of Arc Discharge

ZnO nanorods are fabricated by arc discharge with ZnO powder as source materials. The sample is characterized by x-ray diffraction, Raman scattering spectra, scanning electron microscopy and high-resolution transmission electron microscopy. The ZnO nanorods exhibit single crystals with the hexagonal wurtzite structure. Many of them are tetrapod-like. The diameters range from several nanometres to about lOOnm, and the main diameters of the nanorods is around 20nm. The length-to-diameter ratio is more than 5, and the grown directions are along the [001] axis. Photoluminescence spectra show a narrow ultraviolet emission at around 389nm and a broad green emission at around 520 nm. The growth process can be interpreted by the vapour-solid mechanism.     

制备一维可控形貌的ZnO微米棒

用化学溶液法以醋酸锌和六亚甲基四胺为原料在玻璃衬底上生长出不同形貌的亚微米和微米ZnO棒。探讨了反应液的酸碱度和反应液浓度对生成的ZnO棒形貌的影响，并分析了其生长机制。通过控制一定的酸碱度和溶液浓度，可以得到规则的六角ZnO棒状阵列。这种规则的六角棒沿着[002]方向生长。测量了样品的XRD，扫描电镜像(SEM)，并对其发光性能进行了测量分析。其中规则六角ZnO棒的光致发光光谱中有一很强的峰值650nm红色宽谱带和一峰值约387nm的激子发光峰。激子发光峰加宽，实际上是自由激子的发光峰(380nm)和Zni的发光峰(430nm)的叠加。而红色发光峰可能是Vo2+中的电子和价带中的空穴辐射复合所致。     

Characterization and optical property of ZnO nano-, submicro- and microrods synthesized by hydrothermal method on a large-scale

In the present paper, well-dispersed ZnO nano-, submicro- and microrods with hexagonal structure were synthesized by a simple low temperature hydrothermal process from zinc nitrate hexahydrate without using any additional surfactant, organic solvent or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD), the morphological analysis was carried out by field emission scanning electron microscopy (FESEM) and the optical property was characterized by room-temperature photoluminescence (PL) spectroscopy. The results revealed the high crystal quality of ZnO powder with hexagonal (wurtzite-type) crystal structure and the formation of well-dispersed ZnO nano-, submicro- and microrods with diameters of about 50, 200 and 500 nm, and lengths of 300 nm, 1 μm and 2 μm, respectively, on a large-scale just using the different temperatures. Room-temperature PL spectrum from the ZnO nanorods reveals a strong UV emission peak at about 360 nm and no green emission band at ∼530 nm. The strong UV photoluminescence indicates the good crystallization quality of the ZnO nanorods. Room-temperature PL spectra from the ZnO submicro- and microrods reveal a weak UV emission peak at ∼400 nm and a very strong visible green emission at 530 nm, that is ascribed to the transition between V_oZn_i and valence band.     

Photoluminescence and field emission properties of Sn-doped ZnO microrods

Sn-doped ZnO (SZO) microrods have been fabricated by a thermal evaporation method. Effect of Sn dopant on the microstructure, morphological and composition of as-prepared SZO microrods have been investigated by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The influence of the doping concentration on the morphological of the microrods has been investigated. Photoluminescence (PL) of these SZO microrods exhibits a weak ultraviolet (UV) emission peak at around 382 nm and the strong green emission peak at around 525 nm at room temperature. Field emission measurements demonstrate that the SZO possess good performance with a turn-on field of ∼1.94 V/μm and a threshold field of ∼3.23 V/μm, which have promising application as a competitive cathode material in FE microelectronic devices.     

两步溶液法制备亚微米ZnO棒阵列及其退火后的发光

通过改变溶液浓度、酸碱度等生长条件,用两步化学溶液沉积法在玻璃衬底上制备出有序排列的亚微米级ZnO棒阵列,棒的截面呈正六边形,直径约为200~500nm。测量了样品的XRD谱和扫描电镜像,证明这些样品都是六方纤锌矿结构的ZnO单晶,且以[002]方向择优生长。将样品退火前后的PL光谱进行比较分析,发现退火后样品的发射光谱中紫外峰消失而长波段的红色发光峰红移并且增强(峰位由630nm左右移到720nm),而其激发光谱中的室温激子激发峰也增强。当退火时间增加到6h后,出现了由430nm的蓝峰和505nm绿峰组成的宽谱带蓝绿色发射。并对发光机理进行了讨论。     

Synthesis and luminescent property of single-crystal ZnO nanobelts by a simple low temperature evaporation route

Large-scale ZnO nanobelts in aligned fashion have been prepared via a simply conducted low temperature evaporation route using the oxidization of metallic zinc plates at 450±10 °C under ambient pressure. The produced nanobelt array has been structurally characterized by powder X-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM). The microscope images show that the nanobelts are about 120-micron long, ranging on average from 80 to 160 micron, with about 30 nm in thickness. In addition to XRD, high-resolution TEM images and electron-diffraction patterns show that the nanobelts are single crystalline with wurtzite structure and mostly grow along the [0001] direction. The photoluminescence spectra of the single nanobelts show that the nanobelts have a dominant near-band-edge emission at about 388 nm with a very weak defect emission band centered at about 514 nm. PACS 81.05.Ys; 81.15.Gh; 78.66.Jg     

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     

Induced growth of high quality ZnO thin filmsby crystallized amorphous ZnO

This paper reports the induced growth of high quality ZnO thin film by crystallized amorphous ZnO. Firstly amorphous ZnO was prepared by solid-state pyrolytic reaction, then by taking crystallized amorphous ZnO as seeds (buffer layer), ZnO thin films have been grown in diethyene glycol solution of zinc acetate at 80℃. X-ray Diffraction curve indicates that the films were preferentially oriented [001] out-of-plane direction of the ZnO. Atomic force microscopy and scanning electron microscopy were used to evaluate the surface morphology of the ZnO thin film. Photoluminescence spectrum exhibits a strong ultraviolet emission while the visible emission is very weak. The results indicate that high quality ZnO thin film was obtained.     

一步溶液法制备ZnO亚微米晶体棒及其发光性能

用硝酸锌(Zn(NO₃)₂·4H2O)或醋酸锌(Zn(CH₃COO)₂·2H2O)分别与六亚甲基四胺((CH₂)₆N₄)以等浓度0.005mol/L配制成两种反应溶液,通过化学溶液法在玻璃衬底上生长出ZnO六角型亚微米棒(长5~8μm,直径300~700nm)。测量了样品的XRD和扫描电镜像。经XRD分析,所得样品均为纤锌矿的ZnO六角型晶体。扫描电镜(SEM)像表明,生长时间为3h或5h时,样品为细长条的棒状结构,长径比超过10:1;生长48h后的ZnO亚微米棒的一端被腐蚀成一定深度的ZnO亚微米管。用负离子配位四面体生长模型分析了ZnO亚微米棒的生长机理。ZnO亚微米棒退火前后的光致发光谱表明,退火处理后的发射谱中的紫外峰消失,而红色发光峰红移并且增强(峰值由630nm左右移到710nm),同时它的激发光谱中的室温激子激发峰也增强。     

The growth and optical properties of ZnO nanowires at the junctions of nanowalls

Highly pure ZnO nanowires at the junctions of nanowalls have been successfully prepared via a simple vapor phase route at relative low temperature in the absence of catalyst. SEM, TEM, Raman scattering and PL were employed to characterize as-grown samples. The nanowires have average diameter of 10 nm with [001] growth direction. Raman scattering shifted from higher frequency to lower frequency and the enhancement of PL intensity of the green emission to the UV may be attributed to smaller nanowires and thinner nanowalls. This nanostructure may have important applications in batteries, light-emitting and energy conversion devices and other fields demanding high surface area materials.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

Synthesis and characterization of ZnO columns grown on MgO-coated silicon substrates by carbon-thermal evaporation

Zinc oxide columns have been grown on an MgO-coated silicon (111) substrate by the carbon-thermal evaporation method at 1050 °C. The MgO layer obtained from the substrate pre-dripped in Mg(NO₃)₂ solution by the use of a dropper can solve the troublesome lattice mismatch problem in the heteroepitaxy and promote the growth of ZnO columns effectively. The as-prepared ZnO structures were characterized by using X-ray diffraction (XRD), field-emission transmission electron microscope (FETEM), selection area electron diffraction (SAED), and photoluminescence (PL) spectrum. The results show that the columns are highly crystalline with the wurtzite hexagonal structure, and grow along the [0001] in the c-axis direction. Photoluminescence (PL) spectra of the as-synthesized microstructures exhibit broad green emission peaks at ∼514 nm. In addition, the growth mechanism of the two ZnO structures is discussed based on the analysis briefly based on the time-dependent experiment.     

Synthesis and red-shifted photoluminescence of single-crystalline ZnO nanowires

Local-oriented single-crystalline ZnO nanowires have been synthesized in large scale by a simple microemulsion method in the presence of sulfonate-polystyrene (S-PS) and dodecyl benzene sulfonic acid sodium salt (DBS). The as-prepared product is characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), infrared (IR) spectra and photoluminescence (PL) spectrum. The nanowires exhibit a local congregation and preferentially grow along the [0 0 2] facet. FT-IR spectrum indicates that S-PS is adsorbed on the surface of ZnO nanowires. The PL spectrum shows evidently red-shifted ultraviolet (UV) emission.     

Controllable synthesis and characterization of tube brush-like ZnO nanowires produced via a simple chemical vapor deposition method

Tube brush-like ZnO nanostructures were synthesized by a simple chemical vapor deposition method with Zn and ZnO as precursors. These special ZnO nanostructures were characterized by Scanning Electron Microscope, Energy Dispersive X-ray Spectroscopy, High Resolution Transmission Electron Microscope and Cathodoluminescence (CL) techniques. Empty backbones or comb ribbons backbones were found inside the tube brush-like ZnO structures and fuzzy ZnO nanowires outside. Outside ZnO nanowires grow along the c axis and show green CL emission. The growth mechanism of the hierarchical ZnO nanostructures was investigated by a series of experiments at different growth temperatures and different duration times, and a secondary growth mechanism has been proposed and discussed.