Seed/catalyst-free vertical growth of high-density electrodeposited zinc oxide nanostructures on a single-layer graphene

We report the seed/catalyst-free vertical growth of high-density electrodeposited ZnO nanostructures on a single-layer graphene. The absence of hexamethylenetetramine (HMTA) and heat has resulted in the formation of nanoflake-like ZnO structure. The results show that HMTA and heat are needed to promote the formation of hexagonal ZnO nanostructures. The applied current density plays important role in inducing the growth of ZnO on graphene as well as in controlling the shape, size, and density of ZnO nanostructures. High density of vertically aligned ZnO nanorods comparable to other methods was obtained. The quality of the ZnO nanostructures also depended strongly on the applied current density. The growth mechanism was proposed. According to the growth timing chart, the growth seems to involve two stages which are the formation of ZnO nucleation and the enhancement of the vertical growth of nanorods. ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics such as photovoltaic devices, sensing devices, optical devices, and photodetectors.     

Seed/catalyst-free growth of zinc oxide nanostructures on multilayer graphene by thermal evaporation

We report the seed/catalyst-free growth of ZnO on multilayer graphene by thermal evaporation of Zn in the presence of O₂ gas. The effects of substrate temperatures were studied. The changes of morphologies were very significant where the grown ZnO structures show three different structures, i.e., nanoclusters, nanorods, and thin films at 600°C, 800°C, and 1,000°C, respectively. High-density vertically aligned ZnO nanorods comparable to other methods were obtained. A growth mechanism was proposed based on the obtained results. The ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics.     

Synthesis of zinc oxide nanostructures on graphene/glass substrate by electrochemical deposition: effects of current density and temperature

The electrochemical growth of zinc oxide (ZnO) nanostructures on graphene on glass using zinc nitrate hexahydrate was studied. The effects of current densities and temperatures on the morphological, structural, and optical properties of the ZnO structures were studied. Vertically aligned nanorods were obtained at a low temperature of 75°C, and the diameters increased with current density. Growth temperature seems to have a strong effect in generating well-defined hexagonal-shape nanorods with a smooth top edge surface. A film-like structure was observed for high current densities above -1.0 mA/cm² and temperatures above 80°C due to the coalescence between the neighboring nanorods with large diameter. The nanorods grown at a temperature of 75°C with a low current density of -0.1 mA/cm² exhibited the highest density of 1.45 × 10⁹ cm^-2. X-ray diffraction measurements revealed that the grown ZnO crystallites were highly oriented along the c-axis. The intensity ratio of the ultraviolet (UV) region emission to the visible region emission, I_UV/I_VIS, showed a decrement with the current densities for all grown samples. The samples grown at the current density below -0.5 mA/cm² showed high I_UV/I_VIS values closer to or higher than 1.0, suggesting their fewer structural defects. For all the ZnO/graphene structures, the high transmittance up to 65% was obtained at the light wavelength of 550 nm. Structural and optical properties of the grown ZnO structures seem to be effectively controlled by the current density rather than the growth temperature. ZnO nanorod/graphene hybrid structure on glass is expected to be a promising structure for solar cell which is a conceivable candidate to address the global need for an inexpensive alternative energy source.     

High-performance solid-state supercapacitors based on graphene-ZnO hybrid nanocomposites

In this paper, we report a facile low-cost synthesis of the graphene-ZnO hybrid nanocomposites for solid-state supercapacitors. Structural analysis revealed a homogeneous distribution of ZnO nanorods that are inserted in graphene nanosheets, forming a sandwiched architecture. The material exhibited a high specific capacitance of 156 F g⁻¹ at a scan rate of 5 mV.s⁻¹. The fabricated solid-state supercapacitor device using these graphene-ZnO hybrid nanocomposites exhibits good supercapacitive performance and long-term cycle stability. The improved supercapacitance property of these materials could be ascribed to the increased conductivity of ZnO and better utilization of graphene. These results demonstrate the potential of the graphene-ZnO hybrid nanocomposites as an electrode in high-performance supercapacitors.     

Efficiency improvement of GaN-based ultraviolet light-emitting diodes with reactive plasma deposited AlN nucleation layer on patterned sapphire substrate

The flip chip ultraviolet light-emitting diodes (FC UV-LEDs) with a wavelength of 365 nm are developed with the ex situ reactive plasma deposited (RPD) AlN nucleation layer on patterned sapphire substrate (PSS) by an atmospheric pressure metal-organic chemical vapor deposition (AP MOCVD). The ex situ RPD AlN nucleation layer can significantly reduce dislocation density and thus improve the crystal quality of the GaN epitaxial layers. Utilizing high-resolution X-ray diffraction, the full width at half maximum of the rocking curve shows that the crystalline quality of the epitaxial layer with the (RPD) AlN nucleation layer is better than that with the low-temperature GaN (LT-GaN) nucleation layer. The threading dislocation density (TDD) is estimated by transmission electron microscopy (TEM), which shows the reduction from 6.8 × 10⁷ cm⁻² to 2.6 × 10⁷ cm⁻². Furthermore, the light output power (LOP) of the LEDs with the RPD AlN nucleation layer has been improved up to 30 % at a forward current of 350 mA compared to that of the LEDs grown on PSS with conventional LT-GaN nucleation layer.     

Role of vanadium ions,oxygen vacancies,and interstitial zinc in room temperature ferromagnetism on ZnO-V2O5 nanoparticles

In this work, we present the role of vanadium ions (V⁺⁵ and V⁺³), oxygen vacancies (V_O), and interstitial zinc (Zn_i) to the contribution of specific magnetization for a mixture of ZnO-V₂O₅ nanoparticles (NPs). Samples were obtained by mechanical milling of dry powders and ethanol-assisted milling for 1 h with a fixed atomic ratio V/Zn?=?5% at. For comparison, pure ZnO samples were also prepared. All samples exhibit a room temperature magnetization ranging from 1.18?×?10⁻³ to 3.5?×?10⁻³ emu/gr. Pure ZnO powders (1.34?×?10⁻³ emu/gr) milled with ethanol exhibit slight increase in magnetization attributed to formation of Zn_i, while dry milled ZnO powders exhibit a decrease of magnetization due to a reduction of V_O concentration. For the ZnO-V₂O₅ system, dry milled and thermally treated samples under reducing atmosphere exhibit a large paramagnetic component associated to the formation of V₂O₃ and secondary phases containing V⁺³ ions; at the same time, an increase of V_O is observed with an abrupt fall of magnetization to σ?~?0.7?×?10⁻³ emu/gr due to segregation of V oxides and formation of secondary phases. As mechanical milling is an aggressive synthesis method, high disorder is induced at the surface of the ZnO NPs, including V_O and Zn_i depending on the chemical environment. Thermal treatment restores partially structural order at the surface of the NPs, thus reducing the amount of Zn_i at the same time that V₂O₅ NPs segregate reducing the direct contact with the surface of ZnO NPs. Additional samples were milled for longer time up to 24 h to study the effect of milling on the magnetization; 1-h milled samples have the highest magnetizations. Structural characterization was carried out using X-ray diffraction and transmission electron microscopy. Identification of V_O and Zn_i was carried out with Raman spectra, and energy-dispersive X-ray spectroscopy was used to verify that V did not diffuse into ZnO NPs as well to quantify O/Zn ratios.     

A novel lithium/sulfur battery based on sulfur/graphene nanosheet composite cathode and gel polymer electrolyte

A novel sulfur/graphene nanosheet (S/GNS) composite was prepared via a simple ball milling of sulfur with commercial multi-layer graphene nanosheet, followed by a heat treatment. High-resolution transmission and scanning electronic microscopy observations showed the formation of irregularly interlaced nanosheet-like structure consisting of graphene with uniform sulfur coating on its surface. The electrochemical properties of the resulting composite cathode were investigated in a lithium cell with a gel polymer electrolyte (GPE) prepared by trapping 1 mol dm⁻³ solution of lithium bistrifluoromethanesulfonamide in tetraethylene glycol dimethyl ether in a polymer matrix composed of poly(vinylidene fluoride-co-hexafluoropropylene)/poly(methylmethacrylate)/silicon dioxide (PVDF-HFP/PMMA/SiO₂). The GPE battery delivered reversible discharge capacities of 809 and 413 mAh g⁻¹ at the 1st and 50th cycles at 0.2C, respectively, along with a high coulombic efficiency over 50 cycles. This performance enhancement of the cell was attributed to the suppression of the polysulfide shuttle effect by a collective effect of S/GNS composite cathode and GPE, providing a higher sulfur utilization.     

Tuning of structural,optical, and magnetic properties of ultrathin and thin ZnO nanowire arrays for nano device applications

One-dimensional (1-D) ultrathin (15 nm) and thin (100 nm) aligned 1-D (0001) and (0001¯) oriented zinc oxide (ZnO) nanowire (NW) arrays were fabricated on copper substrates by one-step electrochemical deposition inside the pores of polycarbonate membranes. The aspect ratio dependence of the compressive stress because of the lattice mismatch between NW array/substrate interface and crystallite size variations is investigated. X-ray diffraction results show that the polycrystalline ZnO NWs have a wurtzite structure with a = 3.24 Å, c = 5.20 Å, and [002] elongation. HRTEM and SAED pattern confirmed the polycrystalline nature of ultrathin ZnO NWs and lattice spacing of 0.58 nm. The crystallite size and compressive stress in as-grown 15- and 100-nm wires are 12.8 nm and 0.2248 GPa and 22.8 nm and 0.1359 GPa, which changed to 16.1 nm and 1.0307 GPa and 47.5 nm and 1.1677 GPa after annealing at 873 K in ultrahigh vacuum (UHV), respectively. Micro-Raman spectroscopy showed that the increase in E₂ (high) phonon frequency corresponds to much higher compressive stresses in ultrathin NW arrays. The minimum-maximum magnetization magnitude for the as-grown ultrathin and thin NW arrays are approximately 8.45 × 10⁻³ to 8.10 × 10⁻³ emu/g and approximately 2.22 × 10⁻⁷ to 2.190 × 10⁻⁷ emu/g, respectively. The magnetization in 15-nm NW arrays is about 4 orders of magnitude higher than that in the 100 nm arrays but can be reduced greatly by the UHV annealing. The origin of ultrathin and thin NW array ferromagnetism may be the exchange interactions between localized electron spin moments resulting from oxygen vacancies at the surfaces of ZnO NWs. The n-type conductivity of 15-nm NW array is higher by about a factor of 2 compared to that of the 100-nm ZnO NWs, and both can be greatly enhanced by UHV annealing. The ability to tune the stresses and the structural and relative occupancies of ZnO NWs in a wide range by annealing has important implications for the design of advanced photonic, electronic, and magneto-optic nano devices.     

Effect of ZnO:Cs2CO3 on the performance of organic photovoltaics

We demonstrate a new solution-processed electron transport layer (ETL), zinc oxide doped with cesium carbonate (ZnO:Cs₂CO₃), for achieving organic photovoltaics (OPVs) with good operational stability at ambient air. An OPV employing the ZnO:Cs₂CO₃ ETL exhibits a fill factor of 62%, an open circuit voltage of 0.90 V, and a short circuit current density of −6.14 mA/cm² along with 3.43% power conversion efficiency. The device demonstrated air stability for a period over 4 weeks. In addition, we also studied the device structure dependence on the performance of organic photovoltaics. Thus, we conclude that ZnO:Cs₂CO₃ ETL could be employed in a suitable architecture to achieve high-performance OPV.     

Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays

High density ZnO nanorod arrays were grown on Si substrates coated with ZnO seed layers via aqueous solution route. The ZnO seed layers were deposited on the substrate using DC reactive sputtering and RF magnetron sputtering. It was found that ZnO seed layer with (1 0 3) preferred orientation, prepared using DC reactive sputtering, did not facilitate the formation of ZnO nanorods in the solution grown process. Prior seeding of the surface by ZnO layer with (0 0 2) preferred orientation, deposited using RF magnetron sputtering, leads to nucleation sites on which ZnO nanorod arrays can grow in a highly aligned fashion. ZnO nanorods with well-defined hexagonal facets (0 0 2) were grown almost vertically over the entire substrate. The uniformity and alignment of the nanorod arrays are strongly related to the properties of underneath ZnO seed layers.     

Thermal conductivity reduction of crystalline silicon by high-pressure torsion

We report a dramatic and irreversible reduction in the lattice thermal conductivity of bulk crystalline silicon when subjected to intense plastic strain under a pressure of 24 GPa using high-pressure torsion (HPT). Thermal conductivity of the HPT-processed samples were measured using picosecond time domain thermoreflectance. Thermal conductivity measurements show that the HPT-processed samples have a lattice thermal conductivity reduction by a factor of approximately 20 (from intrinsic single crystalline value of 142 Wm⁻¹ K⁻¹ to approximately 7.6 Wm⁻¹ K⁻¹). Thermal conductivity reduction in HPT-processed silicon is attributed to the formation of nanograin boundaries and metastable Si-III/XII phases which act as phonon scattering sites, and because of a large density of lattice defects introduced by HPT processing. Annealing the samples at 873 K increases the thermal conductivity due to the reduction in the density of secondary phases and lattice defects.     

A catalyst-free growth of aluminum-doped ZnO nanorods by thermal evaporation

The growth of Al:ZnO nanorods on a silicon substrate using a low-temperature thermal evaporation method is reported. The samples were fabricated within a horizontal quartz tube under controlled supply of O₂ gas where Zn and Al powders were previously mixed and heated at 700°C. This allows the reactant vapors to deposit onto the substrate placed vertically above the source materials. Both the undoped and doped samples were characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL) measurements. It was observed that randomly oriented nanowires were formed with varying nanostructures as the dopant concentrations were increased from 0.6 at.% to 11.3 at.% with the appearance of ‘pencil-like’ shape at 2.4 at.%, measuring between 260 to 350 nm and 720 nm in diameter and length, respectively. The HRTEM images revealed nanorods fringes of 0.46 nm wide, an equivalent to the lattice constant of ZnO and correspond to the (0001) fringes with regard to the growth direction. The as-prepared Al:ZnO samples exhibited a strong UV emission band located at approximately 389 nm (E _g  = 3.19 eV) with multiple other low intensity peaks appeared at wavelengths greater than 400 nm contributed by oxygen vacancies. The results showed the importance of Al doping that played an important role on the morphology and optical properties of ZnO nanostructures. This may led to potential nanodevices in sensor and biological applications.     

Selective growth of ZnO nanorods on microgap electrodes and their applications in UV sensors

Selective area growth of ZnO nanorods is accomplished on microgap electrodes (spacing of 6 μm) by using a facile wet chemical etching process. The growth of ZnO nanorods on a selected area of microgap electrode is carried out by hydrothermal synthesis forming nanorod bridge between two electrodes. This is an attractive, genuine, direct, and highly reproducible technique to grow nanowire/nanorod onto the electrodes on selected area. The ZnO nanorods were grown at 90°C on the pre-patterned electrode system without destroying the electrode surface structure interface and geometry. The ZnO nanorods were tested for their application in ultraviolet (UV) sensors. The photocurrent-to-dark (Iph/Id) ratio was 3.11. At an applied voltage of 5 V, the response and recovery time was 72 and 110 s, respectively, and the response reached 2 A/W. The deposited ZnO nanorods exhibited a UV photoresponse that is promising for future cost-effective and low-power electronic UV-sensing applications.     

Structural,electrical, and optical properties of Ti-doped ZnO films fabricated by atomic layer deposition

High-quality Ti-doped ZnO films were grown on Si, thermally grown SiO₂, and quartz substrates by atomic layer deposition (ALD) at 200°C with various Ti doping concentrations. Titanium isopropoxide, diethyl zinc, and deionized water were sources for Ti, Zn, and O, respectively. The Ti doping was then achieved by growing ZnO and TiO₂ alternately. A hampered growth mode of ZnO on TiO₂ layer was confirmed by comparing the thicknesses measured by spectroscopic ellipsometry with the expected. It was also found that the locations of the (100) diffraction peaks shift towards lower diffraction angles as Ti concentration increased. For all samples, optical transmittance over 80% was obtained in the visible region. The sample with ALD cycle ratio of ZnO/TiO₂ being 20 had the lowest resistivity of 8.874 × 10⁻⁴ Ω cm. In addition, carrier concentration of the prepared films underwent an evident increase and then decreased with the increase of Ti doping concentration.     

Heterogeneous nucleation of β-type precipitates on nanoscale Zr-rich particles in a Mg-6Zn-0.5Cu-0.6Zr alloy

Zirconium (Zr) is an important alloying element to Mg-Zn-based alloy system. In this paper, we report the formation of the β-type precipitates on the nanoscale Zr-rich particles in a Mg-6Zn-0.5Cu-0.6Zr alloy during ageing at 180°C. Scanning transmission electron microscopy examinations revealed that the nanoscale Zr-rich [0001]_α rods/laths are dominant in the Zr-rich core regions of the as-quenched sample after a solution treatment at 430°C. More significantly, these Zr-rich particles served as favourable sites for heterogeneous nucleation of the Zn-rich β-type phase during subsequent isothermal ageing at 180°C. This research provides a potential route to engineer precipitate microstructure for better strengthening effect in the Zr-containing Mg alloys.     

Growth of ZnO nanostructures: Cones,rods and hallow-rods,by microwave assisted wet chemical growth and their characterization

ZnO nanostructures were grown by microwave assisted wet-chemical growth, at different microwave powers and for different growth durations. The grown nanostructures were analysed for their morphological, structural, compositional and optical characteristics. The total microwave power per growth run (product of microwave power and growth duration, with units in watt-min), has a linear relationship with most of the characteristics of the grown ZnO nanostructures. It is shown that by altering the microwave power per growth run, the morphology of the individual ZnO nanostructure can be changed from cones with hexagonal cross section, to faceted hexagonal nanorods, to hollow hexagonal nanorods. It is observed that, while the fast growth rate along the high energy polar faces (0001) and (000ī) of ZnO is the reason behind the formation of one dimensional ZnO structures (cones and rods), the process of formation of hallow ZnO rods is due to further etching/material-removal from the tip of the rods, at high microwave power conditions at long growth durations.     

Realization of radial p-n junction silicon nanowire solar cell based on low-temperature and shallow phosphorus doping

A radial p-n junction solar cell based on vertically free-standing silicon nanowire (SiNW) array is realized using a novel low-temperature and shallow phosphorus doping technique. The SiNW arrays with excellent light trapping property were fabricated by metal-assisted chemical etching technique. The shallow phosphorus doping process was carried out in a hot wire chemical vapor disposition chamber with a low substrate temperature of 250°C and H₂-diluted PH₃ as the doping gas. Auger electron spectroscopy and Hall effect measurements prove the formation of a shallow p-n junction with P atom surface concentration of above 10²⁰ cm⁻³ and a junction depth of less than 10 nm. A short circuit current density of 37.13 mA/cm² is achieved for the radial p-n junction SiNW solar cell, which is enhanced by 7.75% compared with the axial p-n junction SiNW solar cell. The quantum efficiency spectra show that radial transport based on the shallow phosphorus doping of SiNW array improves the carrier collection property and then enhances the blue wavelength region response. The novel shallow doping technique provides great potential in the fabrication of high-efficiency SiNW solar cells.     

Enhanced UV photosensitivity from rapid thermal annealed vertically aligned ZnO nanowires

We report on the major improvement in UV photosensitivity and faster photoresponse from vertically aligned ZnO nanowires (NWs) by means of rapid thermal annealing (RTA). The ZnO NWs were grown by vapor-liquid-solid method and subsequently RTA treated at 700°C and 800°C for 120 s. The UV photosensitivity (photo-to-dark current ratio) is 4.5 × 10³ for the as-grown NWs and after RTA treatment it is enhanced by a factor of five. The photocurrent (PC) spectra of the as-grown and RTA-treated NWs show a strong peak in the UV region and two other relatively weak peaks in the visible region. The photoresponse measurement shows a bi-exponential growth and bi-exponential decay of the PC from as-grown as well as RTA-treated ZnO NWs. The growth and decay time constants are reduced after the RTA treatment indicating a faster photoresponse. The dark current-voltage characteristics clearly show the presence of surface defects-related trap centers on the as-grown ZnO NWs and after RTA treatment it is significantly reduced. The RTA processing diminishes the surface defect-related trap centers and modifies the surface of the ZnO NWs, resulting in enhanced PC and faster photoresponse. These results demonstrated the effectiveness of RTA processing for achieving improved photosensitivity of ZnO NWs.     

Room-temperature nonequilibrium growth of controllable ZnO nanorod arrays

In this study, controllable ZnO nanorod arrays were successfully synthesized on Si substrate at room temperature (approx. 25°C). The formation of controllable ZnO nanorod arrays has been investigated using growth media with different concentrations and molar ratios of Zn(NO₃)₂ to NaOH. Under such a nonequilibrium growth condition, the density and dimension of ZnO nanorod arrays were successfully adjusted through controlling the supersaturation degree, i.e., volume of growth medium. It was found that the wettability and electrowetting behaviors of ZnO nanorod arrays could be tuned through variations of nanorods density and length. Moreover, its field emission property was also optimized by changing the nanorods density and dimension.     

Electrical and optical properties of Al-doped ZnO and ZnAl2O4 films prepared by atomic layer deposition

ZnO/Al₂O₃ multilayers were prepared by alternating atomic layer deposition (ALD) at 150°C using diethylzinc, trimethylaluminum, and water. The growth process, crystallinity, and electrical and optical properties of the multilayers were studied with a variety of the cycle ratios of ZnO and Al₂O₃ sublayers. Transparent conductive Al-doped ZnO films were prepared with the minimum resistivity of 2.4 × 10⁻³ Ω·cm at a low Al doping concentration of 2.26%. Photoluminescence spectroscopy in conjunction with X-ray diffraction analysis revealed that the thickness of ZnO sublayers plays an important role on the priority for selective crystallization of ZnAl₂O₄ and ZnO phases during high-temperature annealing ZnO/Al₂O₃ multilayers. It was found that pure ZnAl₂O₄ film was synthesized by annealing the specific composite film containing alternative monocycle of ZnO and Al₂O₃ sublayers, which could only be deposited precisely by utilizing ALD technology.