Periodically Aligned Si Nanopillar Arrays as Efficient Antireflection Layers for Solar Cell Applications

Periodically aligned Si nanopillar (PASiNP) arrays were fabricated on Si substrate via a silver-catalyzed chemical etching process using the diameter-reduced polystyrene spheres as mask. The typical sub-wavelength structure of PASiNP arrays had excellent antireflection property with a low reflection loss of 2.84% for incident light within the wavelength range of 200–1,000 nm. The solar cell incorporated with the PASiNP arrays exhibited a power conversion efficiency (PCE) of ~9.24% with a short circuit current density (J _SC ) of ~29.5 mA/cm² without using any extra surface passivation technique. The high PCE of PASiNP array-based solar cell was attributed to the excellent antireflection property of the special periodical Si nanostructure.     

Fabrication of Antireflective Sub-Wavelength Structures on Silicon Nitride Using Nano Cluster Mask for Solar Cell Application

We have developed a simple and scalable approach for fabricating sub-wavelength structures (SWS) on silicon nitride by means of self-assembled nickel nanoparticle masks and inductively coupled plasma (ICP) ion etching. Silicon nitride SWS surfaces with diameter of 160–200 nm and a height of 140–150 nm were obtained. A low reflectivity below 1% was observed over wavelength from 590 to 680 nm. Using the measured reflectivity data in PC1D, the solar cell characteristics has been compared for single layer anti-reflection (SLAR) coatings and SWS and a 0.8% improvement in efficiency has been seen.     

High Aspect Ratio Polymeric Nanoneedle Arrays

High aspect ratio (HAR) nanoneedle arrays can be used to tune the intrinsic properties of substrates such as their wettability and reflectivity. Here, a simple and scalable fabrication method for producing dense arrays of freestanding polyethylene glycol (PEG) nanoneedles with sub 50 nm tips and surface coverage up to 83 needles per µm² is presented. Two distinct sets of silicon nanoneedle master arrays with base diameters between 15 and 265 nm and heights between 146 and 613 nm are fabricated using block copolymer micelle lithography. Replication of selected silicon masters using photocurable polymers produces HAR PEG nanoneedle arrays with feature base diameters ranging between 15 and 292 nm and heights between 133 and 656 nm. At their maximum, the aspect ratio of the pillars is 4.6. PEG nanoneedle arrays are produced using polymers with two different molecular weights as well as two different photoinitiators, showing the versatility of the process.     

Direct patterning of vertically aligned carbon nanotube arrays to 20 μm pitch using focused laser beam micromachining

We present a scalable approach for the fabrication of large-area arrays of carbon nanotube (CNT) structures using focused laser beams in the 0.05–10 W range. We show that CNT films can easily be micromachined into arrays of columns using a wide variety of commercially available pulsed lasers – Excimer, diode-pumped solid-state (DPSS), and CO₂ – operating at wavelengths from 248 nm to 9300 nm. We demonstrate that vertically aligned carbon nanotube (VACNT) arrays with pitches from 20 to 500 μm can be produced with aspect ratios greater than 20:1. Machining speeds up to 425 mm/s were demonstrated and trenches were produced from 10 to 200 μm wide depending on the laser method and beam size. The CO₂ laser had the largest beam diameter of 175 μm and produced the widest columns with the most taper. The remaining lasers, having beam diameters between 10 and 100 μm, produced smaller columns and finer pitch arrays. The VACNT arrays were shown to have high surface quality with no observable residue left behind, demonstrating focused laser micromachining as a readily available soft tooling means for direct manufacturing of VACNT devices. Laser micromachining methods are compared to evaluate the tradeoffs between quality and manufacturing costs.     

Carbon nanotubes prepared from three-layered copolymer microspheres of acrylonitrile and methylmethacrylate

Carbon nanotubes (CNTs) were synthesized from fine three-layered copolymer microspheres using the polymer blend technique. Diameter of PMMA core/Poly(AN-co-MMA) shell-1/PMMA shell-2 microspheres, prepared by a radical soap-free emulsion polymerization of methylmethacrylate (MMA) and acrylonitrile (AN), was between 400 nm and 500 nm. Microspheres were subjected to melt-spinning at 305 °C, stabilizing in oxygen at 220 °C for 4 h, and finally carbonizing at 1000 °C for 30 min. FE-SEM study of carbonized sample revealed the presence of CNTs arrays on carbon blocks. Similar arrays were observed in a comparative CNTs sample prepared from three-layered microspheres with the pure PAN shells-1 layers. HRTEM showed that the CNTs derived from copolymer microspheres had different structure when compared to the control sample, i.e. CNTs often adhered to each other and contained the internal compartments. The insufficient PMMA shell-2 coating of copolymer microspheres is believed to be a reason for CNTs adhesion. The possible mechanisms of the carbon block formation and the adhesion of CNTs are introduced.     

Synthesis of macroporous poly(styrene-divinyl benzene) microspheres by surfactant reverse micelles swelling method

Macroporous poly(styrene-divinyl benzene) microspheres with pore size of about 500 nm were prepared by a new method, surfactant reverse micelles swelling method. The macroporous microspheres were prepared by convenient suspension polymerization. The difference from conventional suspension polymerization was that a higher concentration of surfactant was added in the oil phase. The effects of the amount and type of surfactants on the morphology of microspheres were investigated, and the formation mechanism was also discussed. Macropores were formed when the concentration of surfactant was much higher than critical micelle concentration (cmc). It was proposed that a large amount of reverse micelles formed by adding a large amount of surfactant in the oil droplet phase, and the reverse micelles could absorb water from the external aqueous phase. The water in the oil phase formed macropores after polymerization. The method developed in this study was convenient to prepare microspheres with larger pore size than the conventional method such as agglomeration method of nanoparticles.     

Fabrication of Highly Ordered Polymeric Nanodot and Nanowire Arrays Templated by Supramolecular Assembly Block Copolymer Nanoporous Thin Films

Realizing the vast technological potential of patternable block copolymers requires both the precise controlling of the orientation and long-range ordering, which is still a challenging topic so far. Recently, we have demonstrated that ordered nanoporous thin film can be fabricated from a simple supramolecular assembly approach. Here we will extend this approach and provide a general route to fabricate large areas of highly ordered polymeric nanodot and nanowire arrays. We revealed that under a mixture solvent annealing atmosphere, a near-defect-free nanoporous thin film over large areas can be achieved. Under the direction of interpolymer hydrogen bonding and capillary action of nanopores, this ordered porous nanotemplate can be properly filled with phenolic resin precursor, followed by curation and pyrolysis at middle temperature to remove the nanotemplate, a perfect ordered polymer nanodot arrays replication was obtained. The orientation of the supramolecular assembly thin films can be readily re-aligned parallel to the substrate upon exposure to chloroform vapor, so this facile nanotemplate replica method can be further extend to generate large areas of polymeric nanowire arrays. Thus, we achieved a successful sub-30 nm patterns nanotemplates transfer methodology for fabricating polymeric nanopattern arrays with highly ordered structure and tunable morphologies.     

One-pot hydrothermal synthesis of nano-sheet assembled NiO/ZnO microspheres for efficient sulfur dioxide detection

The nano-sheet assembled NiO/ZnO microspheres with a diameter of ca. 2 μm have been synthesized via facile hydrothermal method followed by a thermal treatment process. The gas-sensing measurement results show that the sensor using nano-sheet assembled NiO/ZnO microspheres exhibits improved response to sulfur dioxide gas compared with the pure ZnO microspheres sensor. In particular, the sensor with a Ni/Zn molar ratio of 0.5 (0.5 mol% NiO/ZnO) shows high response value (S = 107) and superior selectivity to 10 ppm sulfur dioxide at a low operating temperature of 160 °C and the detection limit of the NiO/ZnO sensor toward sulfur dioxide is down to 1 ppm (S = 6). The enhanced sensing performance is attributed to the formation of p-n heterojunctions on the interface, the catalytic function of NiO and the three-dimensional microspheres composed of the lamellar structure with a large specific surface area. The three-dimensional microspheres provide more active sites for gas adsorption, and the interlayer gap facilitates the diffusion of gas in three-dimensional structure, resulting in high sensitivity and superior selectivity. This work provides a simple method for the synthesis of NiO/ZnO heterojunction microspheres with superior gas-sensing performance, which can be used as a potential material for sulfur dioxide detection.     

Seedless Pattern Growth of Quasi-Aligned ZnO Nanorod Arrays on Cover Glass Substrates in Solution

A hybrid technique for the selective growth of ZnO nanorod arrays on wanted areas of thin cover glass substrates was developed without the use of seed layer of ZnO. This method utilizes electron-beam lithography for pattern transfer on seedless substrate, followed by solution method for the bottom-up growth of ZnO nanorod arrays on the patterned substrates. The arrays of highly crystalline ZnO nanorods having diameter of 60 ± 10 nm and length of 750 ± 50 nm were selectively grown on different shape patterns and exhibited a remarkable uniformity in terms of diameter, length, and density. The room temperature cathodluminescence measurements showed a strong ultraviolet emission at 381 nm and broad visible emission at 585–610 nm were observed in the spectrum.     

Fabrication of porous microspheres and network arrays of Zn–Al hydrotalcite-like compounds on Al substrate via facile hydrothermal method

The porous microspheres and network arrays of Zn–Al hydrotalcite-like compounds were synthesized on Al substrate using sodium oxalate via a facile one-step hydrothermal approach at low temperature (70 °C). The Zn–Al hydrotalcite-like microspheres assembled by numerous interlaced curved nanoplates with thickness of about 50 nm were generated when the concentration of sodium oxalate is 0.21 M. The XRD pattern indicates that the product was of good quality in terms of phase purity and crystallinity. The morphology of Zn–Al hydrotalcite-like compounds and the thickness of nanoplates varied with the concentration of sodium oxalate, which should be attributed to the different nucleation density and growth rate. When the concentration of Zn²⁺ and sodium oxalate was proportionally reduced the low nucleation density and growth caused the formation of porous network arrays. The reaction temperature directly affected the diffusion rates of ions and thus the density of the nucleation and growth is responsible for the morphology change when the reaction temperature is varied. Additionally, the Zn–Al hydrotalcite-like microspheres transformed into porous network arrays when the sodium oxalate was substituted by the equivalent sodium acetate, which should be attributed to the low alkalinity of sodium acetate. The density and thickness of nanoplates composed of the porous network arrays can be effectively tailored by adjusting the concentration of sodium acetate. On the basis of experimental results, the growth mechanism was proposed and discussed.     

Formation of novel mesoporous TiC microspheres through a sol–gel and carbothermal reduction process

Novel mesoporous TiC microspheres with uniform size are synthesized via a sol–gel combined carbothermal reduction process. A microfluidic aerosol nozzle was used to produce droplets which were subsequently dried into gel microspheres under different conditions. The influence of drying temperatures and sol aging time on the diameters of obtained gel microspheres was investigated. The spherical morphology of TiC spheres can be maintained after a two-step heat treatment. Moreover, the TiC microspheres exhibit a high surface area of 267 m²/g and consist of 30–50 nm nano TiC grains and 4.5 nm pores. This unique nanostructure is directly formed from the carbothermal reduction of non-porous and template-free titania/carbon spheres.     

The effect of TiN deposition time on the field-emission performance coated on ZnO nanorod arrays

ZnO nanorod arrays (NRs) with a large number of sharp tips and uniform shapes were grown on the carbon cloth (CC) by a simple hydrothermal method. Titanium nitride (TiN) nanoparticles with various thicknesses were deposited on the ZnO NRs by magnetron sputtering to obtain ZnO/TiN core-shell arrays. Field emission (FE) performance of ZnO NRs show close dependence on TiN coating thickness. The turn-on field first decreases and then increases with increasing TiN coating thickness from 60 nm to 300 nm. The arrays with a design architecture can strike a balance between increased emission sites and limited field shielding effects. ZnO/TiN240 core-shell NRs have the lower turn-on electric field at 0.79 V/μm and the higher current densities at 9.39 mA/cm². The field enhancement factor (β) of ZnO/TiN240 is about 3.2 times that of the bare ZnO NRs. On the other hand, the electrochemical properties were improved due to the formation of core-shell heterojunction on the ZnO/TiN interface and porous structure, which makes the ion and charge transport more convenient. Hence, this work not only revealed that the ZnO/TiN core-shell structure exhibited excellent improvement in both FE and supercapacitors applications, but also that growing arrays on CC was expected to achieve flexible display.     

Hydrothermally Grown ZnO Micro/Nanotube Arrays and Their Properties

We reported the optical and wettability properties of aligned zinc oxide micro/nanotube arrays, which were synthesized on zinc foil via a simple hydrothermal method. As-synthesized ZnO micro/nanotubes have uniform growth directions along the [0001] orientations with diameters in the range of 100–700 nm. These micro/nanotubes showed a strong emission peak at 387 nm and two weak emission peaks at 422 and 485 nm, respectively, and have the hydrophobic properties with a contact angle of 121°. Single ZnO micro/nanotube-based field-effect transistor was also fabricated, which shows typical n-type semiconducting behavior.     

Optical properties of Ni and Cu nanowire arrays and Ni/Cu superlattice nanowire arrays

In this study, Ni and Cu nanowire arrays and Ni/Cu superlattice nanowire arrays are fabricated using standard techniques such as electrochemical deposition of metals into porous anodic alumina oxide templates having pore diameters of about 50 nm. We perform optical measurements on these nanowire array structures. Optical reflectance (OR) of the as-prepared samples is recorded using an imaging spectrometer in the wavelength range from 400 to 2,000 nm (i.e., from visible to near-infrared bandwidth). The measurements are carried out at temperatures set to be 4.2, 70, 150, and 200 K and at room temperature. We find that the intensity of the OR spectrum for nanowire arrays depends strongly on the temperature. The strongest OR can be observed at about T = 200 K for all samples in visible regime. The OR spectra for these samples show different features in the visible and near-infrared bandwidths. We discuss the physical mechanisms responsible for these interesting experimental findings. This study is relevant to the application of metal nanowire arrays as optical and optoelectronic devices.     

Preparation of 3D flower-like Ti3C2Tx microspheres by W/O emulsion-assisted assembly and their application for supercapacitors

In this study, we proposed in situ controlled preparation of 3D flower-like Ti₃C₂T_x microspheres (FMXMSs) by water-in-oil (W/O) emulsion-assisted assembly. Polyethyleneimine (PEI), as a large molecule, can effectively stabilize the emulsion system. Ethylenediamine (EDA), as a weak cross-link agent, contains rich amino groups, which can effectively induce the assembly of Ti₃C₂T_x in spherical droplets and eventually form 3D flower-like Ti₃C₂T_x microspheres. By adjusting the water-oil volume ratio, the size of micro-emulsion droplets can be controlled, thus the structure and size of microspheres can finally be controlled. The structure has a large specific surface area (108.31 m² g^-1) which can provide an effective ion diffusion pathway. As the supercapacitors electrode, the specific capacitance of FMXMSs is up to 224.57 F g^-1 at 5 mV s^-1 and 193.67 F g^-1 at 0.5 A g^-1. Moreover, they also show good long-term cyclic stability. After 5000 cycles, the specific capacitance does not decay. The results indicate that W/O emulsion-assisted assembly is feasible for preparing MXenes microspheres with high electrochemical performance.     

Synthesis and characterization of microspheres composed of SnO2 nanoparticles processed via a chemical route

SnO₂ microspheres were synthesized by a chemical route, heating the mixed Sn²⁺ and sulfuric acid solution in the presence of pressurized oxygen at 900 °C in a designed calorimetric pump. Phase analysis was carried out by X-ray diffraction (XRD) and the results confirmed the SnO₂ microspheres as a single-phase tetragonal structure. Scanning electron microscopy (SEM) images indicated that these microspheres with average diameters of 0.9 μm were composed of SnO₂ nanoparticles with a diameter of about 4.7 nm and a crystallite size of 3.7 nm, as observed by transmission electron microscope (TEM) and calculated by Scherrer's equation from diffractograms, respectively. The formation mechanism of microspheres composed of SnO₂ nanoparticles and the influence of changes in processing are proposed and explained.     

Microstructure and growth mechanism of multi-layer graphene standing on polycrystalline SiC microspheres

Multi-layer graphene standing on polycrystalline SiC microspheres was prepared by pyrolyzing liquid polysilacarbosilane. The lateral dimension of the multi-layer graphene is ∼100 nm and the average diameter of the microspheres is ∼0.9 μm. The growth of the multi-layer graphene is proposed to be initiated by phase separation of the microspheres, and facilitated with both crystallization inside and chemical vapor deposition outside. This method offers an alternative way to prepare multi-layer graphene on SiC without the need for 4H– or 6H–SiC crystals.     

High thermal conductivity of polyethylene nanowire arrays fabricated by an improved nanoporous template wetting technique

Generally polymer bulk structures and nanostructures are thermally insulative. In this study, we show that an improved nanoporous template wetting technique can prepare thermally conductive polymer nanowire arrays. The thermal conductivities of the fabricated high-density polyethylene (HDPE) nanowire arrays with diameters of 100 nm and 200 nm, measured by a laser flash method, are about 2 orders of magnitude higher than their bulk counterparts. The estimated thermal conductivity of a single HDPE nanowire is as high as 26.5 W/mK at room temperature. The high orientation of chains of the HDPE nanowires may arise from the integrative effects of shear rate, vibrational perturbation, translocation, nanoconfinement and crystallization. Findings in this study provide useful strategies on enhancing the intrinsic thermal properties of polymer nanostructures.     

Huge volume expansion and structural transformation of carbon nanotube aligned arrays during electrical breakdown in vacuum

We observed a huge volume expansion of aligned single walled carbon nanotube (SWCNT) arrays accompanied by structural transformation during electrical breakdown in vacuum. The SWCNT arrays were assembled between prefabricated palladium source and drain electrodes of 2 μm separation on a silicon/silicon dioxide substrate by dielectrophoresis. At high electrical field, the SWCNT arrays erupt into a large mushroom-like structure. Systematic studies with controlled electrical bias show that above a certain field the SWCNTs swell and transform to nanoparticles and flower-like structures with a small volume increase. Further increases in electrical bias and repeated sweeping results in their transformation into amorphous carbon as determined from scanning electron microscopy and transmission electron microscopy (TEM). Cross-sectional studies using a focused ion beam and TEM show the height of a 2–3 nm SWCNT array increased to about 1 μm with a volume increase of ～400 times. Electron energy loss spectroscopy reveals that graphitic sp² networks of SWCNT are transformed predominantly to sp³. The current–voltage measurements also show an increase in the resistance of the transformed structure.