MBE法生长ZnO纳米线阵列的结构和光学性能

在氧等离子体辅助的MBE系统中, 以1 nm厚的Au薄膜为催化剂, 基于气?液?固(VLS)机制实现了低温ZnO纳米线阵列在Si(111)衬底表面的生长. 通过场发射扫描电子显微镜(FE-SEM)可以观察到, ZnO纳米线阵列垂直生长在衬底上, 直径为20~30 nm. X射线衍射(XRD)和高分辨透射电镜(HRTEM)结果表明: ZnO纳米线为六方纤锌矿结构, 具有沿c轴方向的择优取向. 光致发光(PL)谱显示在380 nm附近有强烈ZnO本征发射峰, 475~650 nm可见光区域有较强的缺陷导致的发射峰.     

反应源温度对ZnO纳米线阵列定向性及发光性能的影响

以Au薄膜为催化剂、ZnO与碳混合粉末为反应源,采用碳热还原法在单晶Si衬底上制备了ZnO纳米线阵列.通过扫描电子显微镜( SEM)、X射线衍射仪(XRD)、荧光分光光度计对样品的表征,研究了反应源温度对ZnO纳米线阵列的定向性和光致发光性能的影响.样品在源温度920℃条件下沿(002)方向择优生长,定向性最好,温度过低不利于ZnO纳米线阵列密集生长,而温度过高导致Zn原子二次蒸发,因而也不利于纳米线阵列的定向和择优生长;样品在源温度880℃有最强的近紫外带边发射,表明温度过高和过低都不利于ZnO晶体结构的优化;由于ZnO纳米线在缺氧氛围下生长,氧空位是缺陷存在的主要形式,因此所有样品都有较强的绿光发射.温度升高导致纳米线生长速度提高而增加了氧空位缺陷数量,从而使样品绿峰强度增强并在源温度920℃时达最大值,但温度的进一步升高可导致ZnO纳米线表面Zn元素的蒸发而降低氧空位缺陷的数量,从而抑制绿峰强度.     

氮掺杂ZnO纳米阵列的制备和电学特性

采用化学气相沉积 （CVD） 法,以高纯ZnO和活性C混合粉末为原料,以NH3为掺杂气体,在Si （111）衬底上制备了N掺杂的ZnO纳米线阵列,用X射线衍射仪 （XRD）、扫描电镜 （SEM）、拉曼光谱对样品进行分析,结果表明, 氮气的掺杂过程对生长N掺杂的ZnO纳米线阵列有一定的影响。除此之外,N掺杂的ZnO纳微米p-n结被合成,表现出很明显的整流特性。     

Facile route to well-aligned ZnO nanowire arrays

Well-aligned ZnO nanowire arrays were fabricated on the photoresist SPR6112-B coated (111) Si substrates by a facile vapor transport and condensation method. The structure and growth mechanism of the ZnO nanowire arrays were investigated in detail. It is found that the immiscibility of the zinc oxide-carbon system is responsible for the self-catalysis vapor-liquid-solid (VLS) growth of nanowire arrays. The photoluminescence measurement only presents a strong near-band-edge ultraviolet (UV) emission band centered at 379.6 nm (3.266 eV), exhibiting that the nanowire arrays are of stoichiometric composition and have good optical performance.     

Fabrication of ZnO nanowire arrays by cycle growth in surfactantless aqueous solution and their applications on dye-sensitized solar cells

Large-scale ZnO nanowire arrays vertically aligned on the substrates were achieved from cycle growth without surfactants. The 8 μm long ZnO nanowire arrays were prepared by 20 cycles. The aspect ratio of ZnO nanowire can be increased with increasing the growth cycle. As displayed by microstructures and photoluminescence (PL) analysis, the ZnO nanowire was good single crystal and the defects in the as-prepared ZnO nanowire arrays were controlled at a low concentration. By increasing the length and aspect ratio of ZnO nanowire, the performances of dye-sensitized solar cells based on the ZnO nanowire arrays were improved. As-prepared ZnO nanowire arrays have potential applications in fabricating next generation nanodevices.     

高压PLD法生长p型钠掺杂氧化锌纳米线阵列

采用高压脉冲激光沉积法(HP-PLD)研究了压强、金催化层厚度对钠掺杂氧化锌纳米线(ZnO:Na)生长的影响, 并制备了ZnO:Al薄膜/ZnO:Na纳米线阵列同质pn结器件。实验发现, 当金膜厚度为4.2 nm, 生长压强为3.33×10⁴ Pa, 生长温度为875℃时, 可在单晶Si衬底上生长c轴取向性良好的ZnO纳米线阵列。X射线衍射和X射线光电子能谱综合分析证实了Na元素成功掺入ZnO纳米线晶格中。在低温(15 K)光致发光谱中, 观测到了一系列由Na掺杂ZnO产生引起的受主光谱指纹特征, 如中性受主束缚激子峰(3.356 eV, A0X)、导带电子到受主峰(3.312 eV, (e, A0))和施主受主对发光峰(3.233 eV, DAP)等。通过在ZnO:Al薄膜上生长ZnO:Na纳米线阵列形成同质结, 测得I-V曲线具有明显的整流特性, 证实了ZnO:Na纳米线具有良好的p型导电性能。     

Direct synthesis of ZnO nanowire arrays on Zn foil by a simple thermal evaporation process

ZnO nanowire arrays were synthesized on zinc foil by a simple thermal evaporation process at relatively low temperature. Morphology and size controlled synthesis of the ZnO nanostructures was achieved by variation of the synthesis temperature, reaction time and the surface roughness of the substrate. A gas-solid and self-catalytic liquid-solid mechanism is proposed for the growth of nanowires at different temperatures. High-resolution transmission electron microscopy (HRTEM) showed that the as-grown nanowires were of single crystal hexagonal wurtzite structure, growing along the [101] direction. Photoluminescence exhibited strong UV emission at ～382?nm and a broad green emission at ～513?nm with 325?nm excitation. Raman spectroscopy revealed a phonon confinement effect when compared with results from bulk ZnO. The nanowire arrays also exhibited a field emission property.     

Ultralong zinc-blende ZnS nanowires grown on polar C face of 6H-SiC substrates at low temperatures by metalorganic chemical vapor deposition

Ultralong ZnS nanowires with high purity were grown on Au-coated polar C face of 6H-SiC substrates via metalorganic chemical vapor deposition at low temperatures. The ZnS nanowires have zinc-blende structure and the length is up to tens of micrometers. HRTEM investigations show that the nanowires are well crystalline single crystal grown along [1 1 1] and free of bulk defects. However, sparse straight and curved nanowires with poor crystalline nature are randomly grown on the Au-coated Si face of 6H-SiC substrates. We deduce that the growth of ZnS is related to the substrates and C face can enhance Au-catalytic VLS growth. The CL spectra of an individual nanowire grown on C and Si face reveal different optical properties. Intrinsic sulfur and zinc vacancies are the main reasons for the 458.1 nm and 459.2 nm blue emission detected in the nanowire grown on C face and Si face, respectively. Nevertheless, an unusual green emission at 565.1 nm is observed in the poor crystalline nanowire grown on Si face, which originates from the bulk defects.     

Growth of well-aligned ZnO nanorods using auge catalyst by vapor phase transportation

Well-aligned ZnO nanorods have been achieved using new alloy (AuGe) catalyst. Zn powder was used as a source material and it was transported in a horizontal tube furnace onto an AuGe deposited Si substrates. The structural and optical properties of ZnO nanorods were characterized by scanning electron microscopy, high resolution X-ray diffraction, and photoluminescence. ZnO nanorods grown at 650 degrees C on 53 nm thick AuGe layer show uniform shape with the length of 8 +/- 0.5 microm and the diameter of 150 +/- 5 nm. Also, the tilting angle of ZnO nanorods (+/- 5.5 degrees) is confirmed by HRXRD. High structural quality of the nanorods is conformed by the photoluminescence measurement. All samples show strong UV emission without considerable deep level emission. However, weak deep level emission appears at high (700 degrees C) temperature due to the increase of oxygen desertion.     

Thickness optimized nanocrystalline ZnO-coated silicon nanowires for cold cathode application

Silicon nanowire is an important material for the potential use as a cold cathode, but there are some bottlenecks like oxidation of the surface during field emission thereby degradation of its performance. To compete with carbon based nanostructures in this field the performance of Si nanowires as field emitter should be improved. Here, we report a simple technique for the significant improvement of field emission properties of Si nanowires by ZnO nanoparticle coating. Boron-doped p-type Si wafers were chemically etched to synthesize vertically aligned silicon nanowires and they were coated with different thicknesses of ZnO layer by radio frequency magnetron sputtering technique. The nanostructured thin films were studied by X-ray photoelectron spectroscopy for compositional and valence states information while their morphological information was obtained by a field emission scanning electron microscope and a high resolution transmission electron microscope. The field assisted electron emission performance of Si nanowires significantly improved for the thickness optimized ZnO coating. The photoluminescence spectra showed a peak at ~558 nm assigned to surface defect states of ZnO and the field emission from Si nanowires coated with ZnO for different times were correlated with the surface defect structures. The mechanism of such improvement is also discussed.     

Optical and field-emission properties of ZnO nanostructures deposited using high-pressure pulsed laser deposition

ZnO nanostructures were deposited on GaN (0001), Al2O3 (0001), and Si (100) substrates using a high-pressure pulsed laser deposition (PLD) method. Vertically aligned hexagonal-pyramidal ZnO nanorods were obtained on the Al2O3 and Si substrates whereas interlinked ZnO nanowalls were obtained on the GaN substrates. A growth mechanism has been proposed for the formation of ZnO nanowalls based on different growth rates of ZnO polar and nonpolar planes. Both ZnO nanorods and nanowalls exhibit a strong E2H vibration mode in the micro-Raman spectra. The corresponding fluorescence spectra of ZnO nanorods and nanowalls showed near band emission at 3.28 eV. The ZnO nanorods grown on the Si substrates exhibited better crystalline and optical properties compared with the ZnO structures grown on the GaN and Al2O3 substrates. The high aspect ratio, good vertical alignment, and better crystallinity of the ZnO nanorods with tapered tips exhibited promising field emission performance with a low turn-on field of 2 V/μm, a high current density of 7.7 mA/cm2, and a large field enhancement factor.     

Effects of thermal annealing in oxygen plasma for buffer layers on properties of ZnO thin films

ZnO thin films with ZnO buffer layers were grown by plasma-assisted molecular beam epitaxy (PA-MBE) on p-type Si(100) substrates. Before the growth of the ZnO thin films, the ZnO buffer layers were deposited on the Si substrates for 20 minutes and then annealed at the different substrate temperature ranging from 600 to 800 degrees C in oxygen plasma. The structural and optical properties of the ZnO thin films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and room-temperature (RT) photoluminescence (PL). A narrower full width at half maximum (FWHM) of the XRD spectra for ZnO(002) and a larger grain are observed in the samples with the thermal annealed buffer layers in oxygen plasma, compared to those of the as-grown sample. The surface morphology of the samples is changed from rugged to flat surface. In the PL spectra, near-band edge emission (NBEE) at 3.2 eV (380 nm) and deep-level emission (DLE) around 1.77 to 2.75 eV (700 to 450 nm) are observed. By increasing the annealing temperatures up to 800 degrees C, the PL intensity of the NBEE peak is higher than that of the as-grown sample. These results imply that the structural and optical properties of ZnO thin films are improved by the annealing process.     

Seed-layer controlled synthesis of well-aligned ZnO nanowire arrays via a low temperature aqueous solution method

A simple and controllable method has been developed to synthesize well-aligned ZnO nanowire arrays on silicon and glass substrates in aqueous solution. A thin ZnO seed-layer coated with colloidal ZnO nanocrystals was introduced to control the density and orientation of ZnO nanowires. X-ray diffraction (XRD) and scanning electron microscopy (SEM) result show the high dense and well-aligned character of ZnO nanowires. The photoluminescence (PL) reveals the high crystal quality of the nanowires. It was found that the ZnO seed-layer can effect the size distribution, density and crystal structure of the nanowires. The growth mechanism of ZnO nanowires was also discussed.     

Fabrication and characterization of Mg-doped ZnO nanorod arrays

Photoelectronic characteristics are investigated in well-aligned MgO-coated ZnO nanorods (MgO/ZnO nanocables) grown on Si substrates buffered with ZnO film at a low temperature by solution techniques. Transmission electron microscopy shows that a rough surface was observed for the MgO-coated ZnO nanorods due to deposition of MgO nanoparticles on the surface of the ZnO nanorods. However, after annealed at high temperatures, the surface of the MgO-coated ZnO nanorods was flattened to form Mg-doped ZnO nanorods. Photoluminescence spectra of Mg-doped ZnO nanorods displayed a blue shift of the near-band-edge emission with increasing annealing temperature indicative of an increase in the band gap of the MgZnO alloy due to diffusion of the Mg atoms into the ZnO nanorods. In contrast, no blue shift was detected for the samples annealed in H2/N2 (5%/95%) reduction atmosphere but a blue emission was detected at 800 degrees C, indicating that MgO diffusion process may produce a new luminescent center to emit the blue emission in H2/N2 reduction atmosphere.     

ZnO nanotips and nanorods on carbon nanotube/Si substrates: anomalous p-type like optical properties of undoped ZnO nanotips

ZnO nanotips and nanorods were grown on screen-printed multi-walled carbon nanotube (MWCNT) films via thermal chemical vapor deposition at relative low growth temperatures of 400 and 500?°C. Uniform formation of ZnO nanotips and nanorods occurred on MWCNT-printed Si substrates, but were rarely observed on bare Si substrates at the same growth temperatures. In photoluminescence (PL) measurements, it was found that ZnO nanorods exhibit typical intrinsic optical properties, while ZnO nanotips revealed p-type like luminescence behavior. Acceptor-related emission bands originating from neutral acceptor-bound exciton, free-to-acceptor and donor-acceptor pair transitions are clearly observed in temperature-dependent PL spectra of ZnO nanotips.     

Synthesis and photoluminescence of ZnO nanowires/nanorods

We report growth of ZnO nanowires on various substrates using a vapour phase transport method and show that the growth mechanism is vapour-liquid-solid growth. We present photoluminescence data for samples grown on a-plane sapphire at room and low temperatures indicating that the optical quality of these structures is potentially excellent, with intense emission and narrow bound exciton linewidths. The intensity decays rapidly with increasing temperature, indicating a strong temperature-activated non-radiative mechanism whose origin is unclear. We observe a high energy excitonic emission close to the band edge which we assign to the “surface” exciton in ZnO at ∼3.368 eV. This assignment is consistent with the large surface to volume ratio of the nanowire systems under consideration and also indicates that this large ratio has a significant effect on the luminescence even at low temperatures. These surface effects may also be responsible for the rapid decay of the luminescence with increasing temperature via a temperature-activated surface recombination. The nanowire systems appear to offer the prospect of extremely efficient excitonic emission for device applications, and we note that one of the important aspects of achieving this potential will be control of the surface effects via passivation or other means.     

Growth and optical properties of aluminum-doped zinc oxide nanostructures on flexible substrates in flexible electronics

Undoped ZnO nanowire arrays and Al-doped ZnO nanostructures with nanowires and nanosheets were successfully synthesized on a polyethylene terephthalate substrate using the rapid hydrothermal synthesis. These undoped ZnO nanowire arrays showed close alignment with highly c-axis oriented and well-defined hexagonal facets (001). The coexistence of the nanowires and nanosheets was observed during the introduction of Al ions. The number of nanosheets increased due to the Al doping concentration and the lack of surface energy. The diameter of the nanosheets and the length of nanowire arrays also increased as a function of the growth time. Room-temperature photoluminescence spectra show that the ZnO:Al nanostructures on the ZnO seeded polyethylene terephthalate substrate yield low level of the defect density compared to the ZnO seeded glass substrate to remove post annealing process.     

High density Si/ZnO core/shell nanowire arrays for photoelectrochemical water splitting

Si/ZnO core/shell nanowire (NW) arrays were fabricated using atomic layer deposition of ZnO shell on n-Si NW arrays prepared by metal assisted electroless etching method. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were utilized to characterize the core/shell structures. Water splitting performance of the core/shell structures was preliminarily studied. The Si/ZnO core/shell NW arrays yielded significantly higher photocurrent density than the planar Si/ZnO structure due to their low reflectance and high surface area. The photoelectrochemical efficiency was found to be 0.035 and 0.002 % for 10 μm-long Si/ZnO NW array and planar Si/ZnO sample, respectively. These results suggested that core/shell structure is superior to planar heterojunction for PEC electrode design. We demonstrated the dependence of photocurrent density on the length of the core/shell array, and analyzed the reasons why longer NW arrays could produce higher photocurrent density. The relationship between the thickness of ZnO shell and the photoconversion efficiency of Si/ZnO NW arrays was also discussed. By applying the core/shell structure in electrode design, one may be able to improve the photoelectrochemical efficiency and photovoltaic device performance.     

Structures and field emission characteristics of ion irradiated silicon nanowire arrays

Silicon nanowire (SiNW) arrays irradiated by energetic Si ions were fabricated by metal vapor vacuum arc (MEVVA) ion implantation method. Hetero-structure of amorphous/crystalline nanowire was formed in which structure of the implanted region on the top of the nanowires was amorphous while the structure of unimplanted region on the bottom remained crystal. Field emission (FE) properties of the SiNW arrays could be improved and modulated by different implantation doses. A low turn-on field of 4.63 V/microm was observed in the SiNWs irradiated by 21 keV Si ion with a dose of 7.86 x 10(16)/cm2, and the applied field for the emission current density reaching 100 microA/cm2 is only 5.52 V/microm. The main reason for the efficient emission is attributed to the formation of amorphous SiNWs and structure defects after implantation. The ion irradiated SiNWs after post-annealing at high temperature had better FE property due to eliminating the restrain effect to electrons.     

An advanced fabrication method of highly ordered ZnO nanowire arrays on silicon substrates by atomic layer deposition

In this work, the controlled fabrication of highly ordered ZnO nanowire (NW) arrays on silicon substrates is reported. Si NWs fabricated by a combination of phase shift lithography and etching are used as a template and are subsequently substituted by ZnO NWs with a dry-etching technique and atomic layer deposition. This fabrication technique allows the vertical ZnO NWs to be fabricated on 4 in Si wafers. Room temperature photoluminescence and micro-photoluminescence are used to observe the optical properties of the atomic layer deposition (ALD) based ZnO NWs. The sharp UV luminescence observed from the ALD ZnO NWs is unexpected for the polycrystalline nanostructure. Surprisingly, the defect related luminescence is much decreased compared to an ALD ZnO film deposited at the same time ona plane substrate. Electrical characterization was carried out by using nanomanipulators. With the p-type Si substrate and the n-type ZnO NWs the nanodevices represent p–n NW diodes.The nanowire diodes show a very high breakthrough potential which implies that the ALD ZnO NWs can be used for future electronic applications.