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.     

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.     

General route to vertical ZnO nanowire arrays using textured ZnO seeds

A method for growing vertical ZnO nanowire arrays on arbitrary substrates using either gas-phase or solution-phase approaches is presented. A approximately 10 nm-thick layer of textured ZnO nanocrystals with their c axes normal to the substrate is formed by the decomposition of zinc acetate at 200-350 degrees C to provide nucleation sites for vertical nanowire growth. The nanorod arrays made in solution have a rod diameter, length, density, and orientation desirable for use in ordered nanorod-polymer solar cells.     

Growth of high-aspect ratio horizontally-aligned ZnO nanowire arrays

A method of fabricating horizontally-aligned zinc-oxide (ZnO) nanowire (NW) arrays with full control over the width and length is demonstrated. SEM images reveal the hexagonal structure typical of zinc oxide NWs. Arrays of high-aspect ratio horizontal ZnO NWs are fabricated by making use of the lateral overgrowth from dot patterns created by electron beam lithography (EBL). An array of patterned wires are lifted off and transferred to a flexible PDMS substrate with possible applications in several key nanotechnology areas.     

Partial conversion reaction of ZnO nanowires to ZnSe by a simple selenization method and their photocatalytic activities

A simple novel synthetic method for preparing ZnSe/ZnO heterostructured nanowire (NW) arrays via the selenization of ZnO NWs is reported. A hydrothermally grown ZnO NWs array on a glass substrate was reacted with selenium vapor to generate a 20–30 nm of zincblend ZnSe nanoparticles (NPs) on wurtzite ZnO NWs. A growth mechanism was proposed based on SEM, XRD, and TEM analysis to explain the partial chemical conversion of ZnO NW surfaces into ZnSe NPs. This mechanism is applicable to the synthesis of other chalcogenide compounds. The as-synthesized ZnSe/ZnO heterojunctions showed enhanced UV–visible light absorption properties. The materials exhibited excellent photocatalytic activity toward the decomposition of an organic dye compared to the bare ZnO due to enhanced light absorption and the type-II cascade band structure.     

ZnO纳米线阵列修饰对材料表面浸润性调控

采用溶胶-凝胶法制备了ZnO薄膜,利用溶剂热沉积法获得大面积均匀ZnO纳米线阵列。通过对水在ZnO材料表面的浸润性研究,发现薄膜材料表面的粗糙度对ZnO膜亲水性有增强作用,而周期性ZnO阵列微结构表面可以实现其疏水性质增强效果。同时从理论上分析了这两种现象的物理机制,讨论了空气填隙对ZnO纳米线阵列表面的浸润性质的敏感性。制备出ZnO纳米线阵列的表观接触角约为103°,具有较强的疏水性质,可为进一步的ZnO光流控研究提供实验基础。     

Effect of electroless etching parameters on the growth and reflection properties of silicon nanowires

Vertically aligned silicon nanowire (Si NW) arrays have been fabricated over large areas using an electroless etching (EE) method, which involves etching of silicon wafers in a silver nitrate and hydrofluoric acid based solution. A detailed parametric study determining the relationship between nanowire morphology and time, temperature, solution concentration and starting wafer characteristics (doping type, resistivity, crystallographic orientation) is presented. The as-fabricated Si NW arrays were analyzed by field emission scanning electron microscope (FE-SEM) and a linear dependency of nanowire length to both temperature and time was obtained and the change in the growth rate of Si NWs at increased etching durations was shown. Furthermore, the effects of EE parameters on the optical reflectivity of the Si NWs were investigated in this study. Reflectivity measurements show that the 42.8% reflectivity of the starting silicon wafer drops to 1.3%, recorded for 10 μm long Si NW arrays. The remarkable decrease in optical reflectivity indicates that Si NWs have a great potential to be utilized in radial or coaxial p-n heterojunction solar cells that could provide orthogonal photon absorption and enhanced carrier collection.     

Reshaping the tips of ZnO nanowires by pulsed laser irradiation

Vertically aligned ZnO nanowires have been synthesized by a hydrothermal method. After being irradiated by a short laser pulse, the tips of the as-synthesized ZnO nanowires can be tailored into a spherical shape. Transmission electron microscopy revealed that the spherical tip is a single-crystalline piece connected to the body of the ZnO nanowire, and that the center of the sphere is hollow. The growth mechanism of the hollow ZnO nanospheres is proposed to involve laser-induced ZnO evaporation immediately followed by re-nucleation in a temperature gradient environment. The laser-irradiated ZnO nanowire array shows hydrophobic properties while the original ZnO nanowire array shows hydrophilicity. The as-grown ZnO nanowire arrays with hollow spherical tips can serve as templates to grow ZnO nanowire arrays with very fine tips, which may be a good candidate material for use in field emission and scanning probe microscopy.      

The effect of residual stresses in the ZnO buffer layer on the density of a ZnO nanowire array

Density control is a valuable concern in the research of ZnO nanowire arrays. In this study, unannealed and annealed ZnO thin films were used as substrates to fabricate ZnO nanowire arrays. In the unannealed thin film, an inhomogeneous distribution of the nanowire array was found: the density of nanowires decreases with the increase of distance to the edge. In the annealed thin film, the density of nanowire array becomes larger and more homogeneous. Moreover, nanowires are found in high density along microcracks. It is proposed that the residual stresses in the thin film and the density of the nanowire array are in inverse proportion, leading to the results mentioned above. The relationship between residual stresses and the density of nanowires will have potential applications in modifying the density of ZnO nanowire arrays.     

Ultra-fast microwave-assisted hydrothermal synthesis of long vertically aligned ZnO nanowires for dye-sensitized solar cell application

Long vertically aligned ZnO nanowire arrays were synthesized using an ultra-fast microwave-assisted hydrothermal process. Using this method, we were able to grow ZnO nanowire arrays at an average growth rate as high as 200?nm?min(-1) for maximum microwave power level. This method does not suffer from the growth stoppage problem at long growth times that, according to our investigations, a normal microwave-assisted hydrothermal method suffers from. Longitudinal growth of the nanowire arrays was investigated as a function of microwave power level and growth time using cross-sectional FESEM images of the grown arrays. Effect of seed layer on the alignment of nanowires was also studied. X-ray diffraction analysis confirmed c-axis orientation and single-phase wurtzite structure of the nanowires. J-V curves of the fabricated ZnO nanowire-based mercurochrome-sensitized solar cells indicated that the short-circuit current density is increased with increasing the length of the nanowire array. According to the UV-vis spectra of the dyes detached from the cells, these increments were mainly attributed to the enlarged internal surface area and therefore dye loading enhancement in the lengthened nanowire arrays.     

Layer-by-layer assembly synthesis of ZnO/SnO2 composite nanowire arrays as high-performance anode for lithium-ion batteries

A layer-by-layer approach has been developed to synthesize ZnO/SnO₂ composite nanowire arrays on copper substrate. ZnO nanowire arrays have been first prepared on copper substrate through seed-assisted method, and then, the surface of ZnO nanowires have been modified by the polyelectrolyte. After oxidation-reduction reaction, SnO₂ layer has been deposited onto the surface of ZnO nanowires. The as-synthesized ZnO/SnO₂ composite nanowire arrays have been applied as anode for lithium-ion batteries, which show high reversible capacity and good cycling stability compared to pure ZnO nanowire arrays and SnO₂ nanoparticles. It is believed that the improved performance may be attributed to the high capacity of SnO₂ and the good cycling stability of the array structure on current collector.     

Near UV LEDs made with in situ doped p-n homojunction ZnO nanowire arrays

Catalyst-free p-n homojunction ZnO nanowire (NW) arrays in which the phosphorus (P) and zinc (Zn) served as p- and n-type dopants, respectively, have been synthesized for the first time by a controlled in situ doping process for fabricating efficient ultraviolet light-emitting devices. The doping transition region defined as the width for P atoms gradually occupying Zn sites along the growth direction can be narrowed down to sub-50 nm. The cathodoluminescence emission peak at 340 nm emitted from n-type ZnO:Zn NW arrays is likely due to the Burstein-Moss effect in the high electron carrier concentration regime. Further, the electroluminescence spectra from the p-n ZnO NW arrays distinctively exhibit the short-wavelength emission at 342 nm and the blue shift from 342 to 325 nm is observed as the operating voltage further increasing. The ZnO NW p-n homojunctions comprising p-type segment with high electron concentration are promising building blocks for short-wavelength lighting device and photoelectronics.     

Fabrication of slantingly-aligned silicon nanowire arrays for solar cell applications

Large-area slantingly-aligned silicon nanowire arrays (SA-SiNW arrays) on Si(111) substrate have been fabricated by wet chemical etching with dry metal deposition method and employed in the fabrication of solar cells for the first time. The formation of SA-SiNW arrays possibly results from the anisotropic etching of silicon by silver catalysts. Superior to the previous cells fabricated with vertically-aligned silicon nanowire arrays (VA-SiNW arrays), the SA-SiNW array solar cells exhibit a highest power conversion efficiency of?11.37%. The improved device performance is attributed to the integration of the excellent anti-reflection property of the arrays and the better electrical contact of the cell as a result of the special slantingly-aligned structure. The high surface recombination velocity of minority carriers in SiNW arrays is still the main limitation on cell performance.     

Direct observation of enhanced cathodoluminescence emissions from ZnO nanocones compared with ZnO nanowire arrays

We report, for the first time, direct observation of enhanced cathodoluminescence (CL) emissions from ZnO nanocones (NCs) compared with ZnO nanowires (NWs). For direct and unambiguous comparison of CL emissions from NWs and nanocones, periodic arrays of ZnO NW were converted to nanocone arrays by our unique HCl [aq] etching technique, enabling us to compare the CL emissions from original NWs and final nanocones at the same location. CL measurements on NW and nanocone arrays reveal that emission intensity of the nanocone at ～ 387 nm is over two times larger than that of NW arrays. The enhancement of CL emission from nanocones has been confirmed by finite-difference time-domain simulation of enhanced light extraction from ZnO nanocones compared to ZnO NWs. The enhanced CL from nanocones is attributed to its sharp morphology, resulting in more chances of photons to be extracted at the interface between ZnO and air.     

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as‐deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air‐stable active‐layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water‐repellent ability of the OPV device.     

锰掺杂氧化锌纳米线的制备及其光催化性能

采用水热法制备氧化锌纳米线,并通过降解甲基橙评价其光催化活性。以聚乙二醇为模板,氯化锌和氯化锰为原料,在120℃下能获得具有纤锌立方结构的锰掺杂氧化锌纳米线,直径大约为30nm,改变聚乙二醇和氢氧化钠的量,可获得锰掺杂氧化锌纳米线阵列。此外,相比纳米线阵列,锰掺杂氧化锌纳米线具有更好的光催化性能,在120min能降解浓度为20mg／L的β甲基橙溶液。     

Structure, photoluminescence and wettability properties of well arrayed ZnO nanowires grown by hydrothermal method

Well aligned ZnO nanowire arrays with high crystal quality were grown on Si substrates at a low temperature (50 degrees C) by hydrothermal method using a pre-formed ZnO seed layer. ZnO seeds were prepared via radio-frequency magnetron sputtering onto Si substrates. The morphologies of the ZnO nanowire arrays were shown by field emission scanning electron microscopy. X-ray diffraction spectra showed that the full width at the half maximum of the (0002) peak of the nanowire arrays without any heat treatment was only 0.07 degrees, indicating very high crystal quality. Furthermore, the room-temperature photoluminescence spectra of the ZnO nanowire arrays exhibited excellent UV emission. The special micro/nano surface structure of the ZnO nanowire arrays can enhance the dewettability for surfaces modified via low surface energy materials such as long chain fluorinated organic compounds. The surface of the ZnO nanowire arrays is also found to be superhydrophobic with a contact angle of 165 degrees +/- 1 degrees, while the sliding angle is 3 degrees.     

Synthesis of high crystallinity ZnO nanowire array on polymer substrate and flexible fiber-based sensor

Well aligned ZnO nanowire (NW) arrays are grown on Kevlar fiber and Kapton film via the chemical vapor deposition (CVD) method. These NWs have better crystallinity than those synthesized through the low-temperature hydrothermal method. The average length and diameter of ZnO NWs grown on Kevlar fiber can be controlled from 0.5 to 2.76 μm and 30 to 300 nm, respectively. A flexible ultraviolet (UV) sensor based on Kevlar fiber/ZnO NWs hybrid structure is made to detect UV illumination quantificationally.     

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.     

Ordered ZnO/AZO/PAM nanowire arrays prepared by seed-layer-assisted electrochemical deposition

An Al-doped ZnO (AZO) seed layer is prepared on the back side of a porous alumina membrane (PAM) substrate by spin coating followed by annealing in a vacuum at 400 °C. Zinc oxide in ordered arrays mediated by a high aspect ratio and an ordered pore array of AZO/PAM is synthesized. The ZnO nanowire array is prepared via a 3-electrode electrochemical deposition process using ZnSO₄ and H₂O₂ solutions at a potential of − 1 V (versus saturated calomel electrode) and temperatures of 65 and 80 °C. The microstructure and chemical composition of the AZO seed layer and ZnO/AZO/PAM nanowire arrays are characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and energy-dispersive X-ray spectroscopy (EDS). Results indicate that the ZnO/AZO/PAM nanowire arrays were assembled in the nanochannel of the porous alumina template with diameters of 110–140 nm. The crystallinity of the ZnO nanowires depends on the AZO seed layer during the annealing process. The nucleation and growth process of ZnO/AZO/PAM nanowires are interpreted by the seed-layer-assisted growth mechanism.