Growth of size-tunable periodic Ni silicide nanodot arrays on silicon substrates

The fabrications of size-tunable periodic arrays of nickel metal and silicide nanodots on (0 0 1)Si substrates using polystyrene (PS) nanosphere lithography (NSL) and heat treatments have been investigated. The growth of epitaxial NiSi₂ was found to be more favorable for the Ni metal nanodot arrays. The effect becomes more pronounced with a decrease in the size of the Ni nanodots. The sizes of the epitaxial NiSi₂ nanodots were tuned from 38 to 110 nm by varying the diameter of the PS spheres and heat treatment conditions. These epitaxial NiSi₂ nanodots formed on (0 0 1)Si were found to be heavily faceted and the faceted structures were more prone to form at higher temperatures. Based on TEM, HRTEM and SAED analysis, the faceted NiSi₂ nanodots were identified to be inverse pyramids in shape. Compared with the NiSi₂ nanodot arrays formed using single-layer PS sphere masks, the epitaxial NiSi₂ nanodot arrays formed from the double-layer PS sphere templates exhibit larger interparticle spacings and smaller particle sizes. Since the nanoparticle sizes, shapes and interparticle spacings can be adjusted by tuning the diameter of the PS spheres, stacking conditions, and heat treatment conditions, the PS NSL technique promises to be an effective patterning method for growth of other nanostructures.     

Growth of high-density Ru- and RuO2-composite nanodots on atomic-layer-deposited Al2O3 film

Growth of Ru- and RuO₂-composite (ROC) nanodots on atomic-layer-deposited Al₂O₃ film has been studied for the first time using ion-beam sputtering followed by post-deposition annealing (PDA). X-ray photoelectron spectroscopy analyses reveal that RuO₂ and Ru co-exist before annealing, and around 10% RuO₂ is reduced to metallic Ru after PDA at 900 °C for 15 s. Scanning electron microscopy measurements show that well-defined spherical ROC nanodots are not formed till the PDA temperature is raised to 900 °C. The mean diameter of the nanodots enlarges with increasing PDA temperature whereas the nanodot density decreases, which is attributed to coalescence process between adjacent nanodots. It is further illustrated that the resulting nanodot size and density are weakly dependent on the annealing time, but are markedly influenced by the decomposition of RuO₂. In this article, the ROC nanodots with a high density of 1.6 × 10¹¹ cm⁻², a mean diameter of 20 nm with a standard deviation of 3.0 nm have been achieved for the PDA at 900 °C for 15 s, which is promising for flash memory application.     

Controlled growth and field emission properties of zinc oxide nanopyramid arrays

Single-crystalline, pyramidal zinc oxide nanorods have been synthesized in a large quantity on p-Si substrate via catalyst-free thermal chemical vapor deposition at low temperature. SEM investigations showed that the nanorods were vertically aligned on the substrate, with diameters ranging from 60 to 80 nm and lengths about 1.5 μm. A self-catalysis VLS growth mechanism was proposed for the formation of the ZnO nanorods. The field emission properties of the ZnO nanopyramid arrays were investigated. A turn-on field about 3.8 V/μm was obtained at a current density of 10 μA/cm², and the field emission data was analyzed by applying the Fowler-Nordheim theory. The stability of emission current density under a high voltage was also tested, indicating that the ZnO nanostructures are promising for an application such as field emission sources.     

Growth and field emission properties of nanotip arrays of amorphous carbon with embedded hexagonal diamond nanoparticles

Nanotip arrays of amorphous carbon with embedded hexagonal diamond nanoparticles were prepared at room temperature for use as excellent field emitters by a unique combination of anodic aluminum oxide (AAO) template and filtered cathodic arc plasma (FCAP) technology. In order to avoid nanopore array formation on the AAO surface, an effective multi-step treatment employing anodization and pore-widening processes alternately was adopted. The nanotips were about 100 nm in width at the bottom and 150 nm in height with density up to 10¹⁰ cm⁻². Transmission electron microscopy investigation indicates that many nanoparticles with diameters of about 10 nm were embedded in the amorphous carbon matrix, which was proved to be hexagonal diamond phase by Raman spectrum and selected-area electron diffraction. There is no previous literature report on the field emission properties of hexagonal diamond and its preparation at room temperature under high-vacuum condition. The nanotip arrays with hexagonal diamond phase exhibit a low turn-on field of 0.5 V/μm and a threshold field of 3.5 V/μm at 10 mA/cm². It is believed that the existence of hexagonal diamond phase has improved the field emission properties.     

Electron field emission from a patterned array of diamond-like carbon on anodic aluminum oxide template

A patterned array of diamond-like carbon (DLC) was grown on anodic aluminum oxide (AAO) template by filtered cathodic arc plasma (FCAP) technique at room temperature. The diameters of patterned array of DLC were ∼150 nm, and the patterned array density was estimated to ∼10⁹ cm⁻². A broad asymmetric band ranging from 1000 cm⁻¹ to 2000 cm⁻¹ was detected by Raman spectrum attributed to characteristic band of DLC. The fraction of sp³ bonded carbon atoms of the patterned array of DLC was measured by X-ray photoelectron spectrum (XPS) and the ratio was about 62.4%. Field emission properties of the patterned array of DLC were investigated. A low turn-on field of 3.4 V/μm at 10 μA/cm² with an emission area of 3.14 mm² was achieved. The results indicated that the electrons were emitted under both the effect of enhanced field because of the geometry and the work function of the DLC sample. Based on Fowler-Nordheim plot, the values of work function for the patterned array of DLC were estimated in range of 0.38 to 1.75 from a linearity plot.     

Field emission from awl-shaped diamond-like carbon by using filtered cathodic arc plasma technique on anodic aluminum oxide template

Awl-shaped diamond-like carbon (DLC) was directly grown on anodic aluminum oxide (AAO) template by using filtered cathodic arc plasma (FCAP) technique at room temperature. The awls of DLC were about 250 nm in the height and the diameters of the awls were ∼100 nm at the top. The awl density was estimated to be ∼10⁸ cm⁻². A broad asymmetric band ranging from 1100 to 1800 cm⁻¹ was detected by Raman spectrum. This asymmetric band was characteristic band of DLC. The sp³/(sp³+sp²) ratio of C-C bond of the awl-shaped DLC was measured by X-ray photoelectron spectrum, and it was about 68.3%. Field-emission properties of the awl-shaped DLC were investigated. A low turn-on field of 2.6 V/μm at 10 μA/cm² with an emission area of 3.14 mm² was achieved, and the emission current stability was very good. The results indicated that the electrons were emitted under both the effect of enhanced field because of the geometry and the work function of the DLC sample. Based on Fowler-Nordheim plot, the values of work function for the awl-shaped DLC were estimated in ranges of 0.23-1.08 from a linearity plot.     

Silver nanostructure arrays abundant in sub-5 nm gaps as highly Raman-enhancing substrates

Two types of highly Raman-enhancing arrays substrates were fabricated using anodic aluminum oxide (AAO) templates by controlling the AAO template temperature and evaporated silver thickness during e-beam evaporating: complex patterned Ag nanoparticle arrays abundant in sub-5 nm gaps (type I); hexagonal Ag nanopore arrays (type II). The surface enhanced Raman scattering (SERS) enhancement factors (EF) of both substrates are estimated experimentally to exceed 10⁵, especially that of type I reaches 10⁷ due to the existence of numerous sub-5 nm gaps. The simulation using finite-difference time-domain (FDTD) method confirmed that gap effect has significantly improved the substrates’ SERS activity.     

新型氧化铝模板自组装制备非晶碳纳米点阵列膜及其场发射性能研究

通过对阳极氧化铝(AAO)模板进行特殊扩孔处理,消除了AAO模板中带电阴离子对沉积碳离子的不良影响,利用磁过滤阴极弧等离子体沉积技术成功制备了非晶碳纳米尖点阵列膜.场发射扫描电镜(FESEM)分析表明,经过氧化和扩孔多步处理制备的AAO模板具有特殊的开口结构,制备的非晶碳纳米尖点阵列完整地复制了AAO模板的孔道阵列结构,纳米点排列整齐有序,直径约100nm,密度达1010cm-2,样品的场发射测试显示,非晶碳纳米点阵列具有良好的电子发射性能,发射电流为10mA/cm-2时的阈值电场为3.7V/μm.     

Field electron emission improvement of ZnO nanorod arrays after Ar plasma treatment

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved after radio-frequency (rf) Ar plasma treatment. With Ar plasma treatment for 30 min, flat tops of the as-grown ZnO nanorods have been etched into sharp tips without damaging ZnO nanorod geometrical morphologies and crystallinity. After the Ar ion bombardment, the emission current density increases from 2 to 20 μA cm⁻² at 9.0 V μm⁻¹ with a decrease in turn-on voltage from 7.1 to 4.8 V μm⁻¹ at a current density of 1 μA cm⁻², which demonstrates that the field emission of the as-grown ZnO nanorods has been efficiently enhanced. The scanning electron microscopy (SEM) results, in conjunction with the results of transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence observation, are used to investigate the mechanisms of the field emission enhancement. It is believed that the enhancements can be mainly attributed to the sharpening of rod tops, and the decrease of electrostatic screening effect.     

Enhanced field emission from ZnO nanopencils by using pyramidal Si(1 0 0) substrates

Zinc oxide nanopencil arrays were synthesized on pyramidal Si(1 0 0) substrates via a simple thermal evaporation method. Their field emission properties have been investigated: the turn-on electric field (at the current density of 10 μA/cm²) was about 3.8 V/μm, and the threshold electric field (at the current density of 1 mA/cm²) was 5.8 V/μm. Compared with similar structures grown on flat Si substrates, which were made as references, the pyramidal Si-based ZnO nanopencil arrays appeared to be superior in field emission performance, thus the importance of the non-flat substrates has been accentuated. The pyramidal Si substrates could not only suppress the field screening effect but also improve the field enhancement effect during the field emission process. These findings indicated that using non-flat substrates is an efficient strategy to improve the field emission properties.     

Uniform arrays of carbon nanotubes applied in the field emission devices

Carbon nanotubes(CNTs)were grown into anodic aluminum oxide(AAO)channels by chemical vapor deposition(CVD)using C2H2/N2mixtures as feeding gas,which can be used as field emitters.The bottom surface of AAO template was etched slightly and the tips of CNTs were explored as the field emission arrays which were uniform and vertical.Field emission characterization showed a low turn-on field about 3.25 V/m and high emission current about 30 mA/cm2with the electric field about 4 V/m.These superior field emission characteristics could be attributed to low density of vertical CNTs and higher conductivity of the substrate.     

Electrodeposition and magnetic properties of Ni nanowire arrays on anodic aluminum oxide/Ti/Si substrate

Ni nanowire arrays with different diameters have now been extended to directly fabricate in porous anodic alumina oxide (AAO) templates on Ti/Si substrate by direct current (DC) electrodeposition. An aluminum film is firstly sputter-deposited on a silicon substrate coated with a 300 nm Ti film. AAO/Ti/Si substrate is synthesized by a two-step electrochemical anodization of the aluminum film on the Ti/Si substrate and then used as template to grow Ni nanowire arrays with different diameters. The coercivity and the squareness in parallel direction of Ni nanowires with about 10 nm diameters are 664 Oe and 0.90, respectively. The Ni nanowire arrays fabricated on AAO/Ti/Si substrates should lead to practical applications in ultrahigh-density magnetic storage devices because of the excellent properties.     

Fabrication of Ag nanodot array over large area for surface-enhanced Raman scattering using hybrid nanoimprint mold made from AAO template

We demonstrated the fabrication of dense hexagonal arrays of Ag nanodots over a large area using a novel nanoimprint-based fabrication technique for surface-enhanced Raman spectroscopy. Flexible imprint molds with sub-10 nm features were duplicated from AAO templates using a novel hybrid mold technique. This method solves the nonflatness-induced defect issue in the conventional thermal nanoimprint technique, and allows high-quality duplications of nanometer features from rigid nonflat templates. Moreover, with the help of the excellent tunability of the size of nanoholes on AAO templates, we were able to tune the size of Ag nanodots, and consequently to tailor the resonance frequency of the Ag nanodot arrays. Finally, surface-enhanced Raman scattering of Rhodamine-123 on Ag nanodot arrays was measured, and large signal enhancement was observed on the 70 nm Ag nanodots. We numerically simulated the optical properties of those Ag nanodot arrays, and excellent agreement was found with the experimental results.     

Fabrication and field emission properties of multi-walled carbon nanotube/silicon nanowire array

Silicon nanowire (SiNW) arrays were fabricated on silicon wafers by the metal-assisted chemical etching method. Varied average diameters of SiNW arrays were realized through further treatment in a mixed agent of HF and HNO₃ of certain concentrations. After the treatment, there were more than 93% SiNWs with diameters smaller than 100 nm. The tip of each SiNW was subsequently wrapped with multi-walled carbon nanotubes (MWCNTs) with chemical vapor deposition method. The as-fabricated MWCNT/SiNW arrays were fabricated into electric field emitters, with turn-on field of 2.0 V/μm (current density: 10 μA/cm²), much lower than that of SiNW array (5.0 V/μm). The turn-on electric field of MWCNT/SiNW array decreased with the decreasing of the average diameter of SiNWs, indicating the performance of the field emission is relative to the morphology of SiNWs. As the SiNW array is uniform in height and easy to fabricate, the MWCNT/SiNW array shows potential applications in flat electric display.     

Nonlinear optical properties of periodic gold nanoparticle arrays

Periodic Au nanoparticle arrays were fabricated on silica substrates using nanosphere lithography. The identical single-layer masks were prepared by self-assembly of polystyrene nanospheres with radius R = 350 nm. The structural characterization of nanosphere masks and periodic particle arrays was investigated by atomic force microscopy. The nonlinear optical properties of the Au nanoparticle arrays were determined using a single beam z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that periodic Au nanoparticle arrays exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 6.09 × 10⁻⁶ cm²/kW and β = −1.87 × 10⁻⁶ m/W, respectively.     

Synthesis and magnetic properties of ordered barium ferrite nanowire arrays in AAO template

BaFe₁₂O₁₉ nanowire arrays having single magnetic domain size (≤460 nm) in anodic aluminum oxide (AAO) templates were prepared by sol-gel and self-propagating high-temperature synthesis techniques. The diameter of the nanowire arrays is approximately 70 nm and the length is about 2-4 μm. The specimens were characterized using X-ray diffraction, vibrating sample magnetometer, field emission scan electron microscope, atomic force microscopy and microwave vector network analyzer. The magnetic properties of BaFe₁₂O₁₉ nanowire arrays embedded in AAO templates were measured by VSM with a field up to 1274 KA/m at room temperature. The results indicate that the nanowire arrays exhibit large saturation magnetization and high coercivity in the range of 6000 Oe and an obvious magnetic anisotropy with the easy magnetizing axis along the length of the nanowire arrays, probably due to the shape anisotropy and magneto-crystalline anisotropy. Finally the microwave absorption properties of the nanowires were discussed.     

Field emission properties of polymer-converted carbon films by heat treatment

Carbon films were prepared on single crystal silicon substrates by heat-treatment of a polymer-poly(phenylcarbyne) at 800 °C in Ar atmosphere. The heat-treatment caused the change of the polymer into carbon film, which exhibited good field emission properties. Low turn-on emission field of 4.3 V/μm (at 0.1 μA/cm²) and high emission current density of 250 μA/cm² (at 10 V/μm) were observed for the polymer-converted carbon films. This behavior was demonstrated to be mainly related to the microstructure of the carbon films, which consisted of fine carbon nanoparticles with high sp² bonding. The carbon films, which can be deposited simply with large areas, are promising for practical applications in field emission display.     

Flame synthesis of carbon nanotubes for panel field emission lamp

Multi-walled carbon nanotubes (CNTs) were synthesized on the surfaces of Ni-alloy plated Fe-wires with the diameter of 2 mm using a conventional laboratory ethanol (C₂H₅OH) flame method at 560 °C. SEM showed that the product had bush-shaped micron-structures with diameters from 100 to 450 nm and lengths of over 1.0 μm. TEM revealed that the micron-structures were composed of multi-walled nanotube bundles with the diameters of about 50 nm. The test on the diode configuration field emission of the Fe-wire arrays was performed. The onset electric field was 2.95 V/μm and the emission current can reach 50 mA/cm² at an electric field of 9 V/μm. The average fluctuation of the emission current density was less than 7%. The result suggests that the field emission was uniform and the present technique was feasible to fabricate Panel Field Emission Lamp (PFEL) with arrays of carbon nanotubes. PFEL has the advantages of high luminescence as well as stability, and thus, it can be used to replace ordinary lights.     

High-field electron emission of carbon nanotubes grown on carbon fibers

Carbon nanotubes with uniform density were synthesized on carbon fiber substrate by the floating catalyst method. The morphology and microstructure were characterized by scanning electron microscopy and Raman spectroscopy. The results of field emission showed that the emission current density of carbon nanotubes/carbon fibers was 10 μA/cm² and 1 mA/cm² at the field of 1.25 and 2.25 V/μm, respectively, and the emission current density could be 10 and 81.2 mA/cm² with the field of 4.5 and 7 V/μm, respectively. Using uniform and sparse density distribution of carbon nanotubes on carbon fiber substrate, the tip predominance of carbon nanotubes can be exerted, and simultaneously the effect of screening between adjacent carbon nanotubes on field emission performance can also be effectively decreased. Therefore, the carbon nanotubes/carbon fibers composite should be a good candidate for a cold cathode material.     

Formation of nanodots on oblique ion sputtered InP surfaces

Using a field emission gun based scanning electron microscopy, we report the formation of nanodots on the InP surfaces after bombardment by 100 keV Ar⁺ ions under off-normal ion incidence (30° and 60° with respect to the surface normal) condition in the fluence range of 1 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻². Nanodots start forming after a threshold fluence of about 1 × 10¹⁷ ions cm⁻². It is also seen that although the average dot diameter increases with fluence the average number of dots decreases with increasing fluence. Formation of such nanostructured features is attributed due to ion-beam sputtering. X-ray photoelectron spectroscopy analysis of the ion sputtered surface clearly shows In enrichment of the sputtered InP surface. The observation of growth of nanodots on the Ar⁺-ion sputtered InP surface under the present experimental condition matches well with the recent simulation results based on an atomistic model of sputter erosion.