The fabrication of carbon nanostructures using electron beam resist pyrolysis and nanomachining processes for biosensing applications

We present a facile, yet versatile carbon nanofabrication method using electron beam lithography and resist pyrolysis. Various resist nanopatterns were fabricated using a negative electron beam resist, SAL-601, and they were then subjected to heat treatment in an inert atmosphere to obtain carbon nanopatterns. Suspended carbon nanostructures were fabricated by the wet-etching of an underlying sacrificial oxide layer. Free-standing carbon nanostructures, which contain 130?nm wide, 15?nm thick, and 4?μm long nanobridges, were fabricated by resist pyrolysis and nanomachining processes. Electron beam exposure dose effects on resist thickness and pattern widening were studied. The thickness of the carbon nanostructures was thinned down by etching with oxygen plasma. An electrical biosensor utilizing carbon nanostructures as a conducting channel was studied. Conductance modulations of the carbon device due to streptavidin-biotin binding and pH variations were observed.     

Single-step direct fabrication of pillar-on-pore hybrid nanostructures in anodizing aluminum for superior superhydrophobic efficiency

Conventional electrochemical anodizing processes of metals such as aluminum typically produce planar and homogeneous nanopore structures. If hydrophobically treated, such 2D planar and interconnected pore structures typically result in lower contact angle and larger contact angle hysteresis than 3D disconnected pillar structures and, hence, exhibit inferior superhydrophobic efficiency. In this study, we demonstrate for the first time that the anodizing parameters can be engineered to design novel pillar-on-pore (POP) hybrid nanostructures directly in a simple one-step fabrication process so that superior surface superhydrophobicity can also be realized effectively from the electrochemical anodization process. On the basis of the characteristic of forming a self-ordered porous morphology in a hexagonal array, the modulation of anodizing voltage and duration enabled the formulation of the hybrid-type nanostructures having controlled pillar morphology on top of a porous layer in both mild and hard anodization modes. The hybrid nanostructures of the anodized metal oxide layer initially enhanced the surface hydrophilicity significantly (i.e., superhydrophilic). However, after a hydrophobic monolayer coating, such hybrid nanostructures then showed superior superhydrophobic nonwetting properties not attainable by the plain nanoporous surfaces produced by conventional anodization conditions. The well-regulated anodization process suggests that electrochemical anodizing can expand its usefulness and efficacy to render various metallic substrates with great superhydrophilicity or -hydrophobicity by directly realizing pillar-like structures on top of a self-ordered nanoporous array through a simple one-step fabrication procedure.     

Submicron-patterning of bulk titanium by nanoimprint lithography and reactive ion etching

Nanopatterns on titanium may enhance endosseous implant biofunctionality. To enable biological studies to prove this hypothesis, we developed a scalable method of fabricating nanogrooved titanium substrates. We defined nanogrooves by nanoimprint lithography (NIL) and a subsequent pattern transfer to the surface of ASTM grade 2 bulk titanium applying a soft-mask for chlorine-based reactive ion etching (RIE). With respect to direct write lithographic techniques the method introduced here is fast and capable of delivering uniformly patterned areas of at least 4 cm(2). A dedicated silicon nanostamp process has been designed to generate the required thickness of the soft-mask for the NIL-RIE pattern transfer. Stamps with pitch sizes from 1000 nm down to 300 nm were fabricated using laser interference lithography (LIL) and deep cryogenic silicon RIE. Although silicon nanomachining was proven to produce smaller pitch sizes of 200 nm and 150 nm respectively, successful pattern transfer to titanium was only possible down to a pitch of 300 nm. Hence, the smallest nanogrooves have a width of 140 nm. An x-ray photoelectron spectroscopy study showed that only very few contaminations arise from the fabrication process and a cytotoxicity assay on the nanopatterned surfaces confirmed that the obtained nanogrooved titanium specimens are suitable for in vivo studies in implantology research.     

Highly ordered nanostructures with tunable size, shape and properties: A new way to surface nano-patterning using ultra-thin alumina masks

Large-scale arrays of nanostructures on substrates, such as semiconductor or metal nano-particle arrays, have attracted considerable interest due to their unique physical properties and many potential applications in areas such as electronics, optoelectronics, sensing, high-density storage, and ultra-thin display devices. In the last two decades, the search for a highly efficient and low-cost nano-patterning method in fabricating ordered surface nanostructures with tunable dimensions and properties, has involved interdisciplinary and cross-disciplinary research and development with emerging technologies such as lithographic methods, self-assembly processes, and scanning probe techniques. Here, we review a new surface nano-patterning approach in fabricating ordered nanostructures, in which ultra-thin anodic alumina membranes are used as fabrication masks. Using the method, large-scale arrays of highly ordered nanostructures in the range of square centimeters can be fabricated on any substrate in a massive parallel way. The resulting nanostructures are characterized by highly defined and controllable size, shape, composition, and spacing of the nanostructures. Tuning of the properties of the arrayed nanostructures can be obtained by controlled adjustment of the structural parameters of the arrayed nanostructures. Compared to conventional lithographic methods, the present nano-patterning approach offers attractive advantages, such as large pattern area, high throughput, low equipment costs, and high flexibility and control options for ordered nanostructures with tunable properties. This new non-lithographic nano-patterning approach will be shown to be a general method in fabricating a wide range of ordered surface nanostructures with tunable and unique physical and chemical properties that could be used in the fabrication of nano-devices with high performance and controllability.     

Reduction of interpore distance of anodized aluminum oxide nano pattern by mixed H3PO4:H2SO4 electrolyte

A self-formed and ordered anodized aluminum oxide (AAO) nano pattern has generated considerable interest in both scientific research and commercial application. However, the interpore distance obtainable by AAO is limited by 40-500 nm depending on electrolyte and anodizing voltage. It's believed that below-30 nm AAO pattern is a key technology in the fabrication semiconductor nano structures with enhanced quantum confinement effect, so we worked on the reduction of interpore distance of AAO with a novel electrolyte. AAO nano patterns were fabricated with mixed H2SO4 and H3PO4 as an electrolyte for various voltages and temperatures. The interpore distance and pore diameter of AAO were decreased with reduced anodizing voltage. As a result, an AAO nano pattern with the interpore distance of 27 nm and the pore diameter of 7 nm was obtained. This is the smallest pattern, as long as we know, reported till now with AAO technique. The fabricated AAO pattern could be utilized for uniform and high density quantum dots with increased quantum effect.     

Ru nanostructure fabrication using an anodic aluminum oxide nanotemplate and highly conformal Ru atomic layer deposition

We fabricated metallic nanostructures directly on Si substrates through a hybrid nanoprocess combining atomic layer deposition (ALD) and a self-assembled anodic aluminum oxide (AAO) nanotemplate. ALD Ru films with Ru(DMPD)(EtCp) as a precursor and O(2) as a reactant exhibited high purity and low resistivity with negligible nucleation delay and low roughness. These good growth characteristics resulted in the excellent conformality for nanometer-scale vias and trenches. Additionally, AAO nanotemplates were fabricated directly on Si and Ti/Si substrates through a multiple anodization process. AAO nanotemplates with various hole sizes (30-100?nm) and aspect ratios (2:1-20:1) were fabricated by controlling the anodizing process parameters. The barrier layers between AAO nanotemplates and Si substrates were completely removed by reactive ion etching (RIE) using BCl(3) plasma. By combining the ALD Ru and the AAO nanotemplate, Ru nanostructures with controllable sizes and shapes were prepared on Si and Ti/Si substrates. The Ru nanowire array devices as a platform for sensor devices exhibited befitting properties of good ohmic contact and high surface/volume ratio.     

Characterization of uniformity and reproducibility of photoresist nanomasks fabricated by near-field scanning optical nanolithography

The uniformity and reproducibility of the photoresist nanopatterns fabricated using near-field scanning optical nanolithography (NSOL) are investigated. The nanopatterns could be used as nanomasks for pattern transfer on a silicon wafer. In the NSOL process, uniform patterning with high reproducibility is essential for reliable transfer of the mask patterns on a silicon substrate. Using an aperture type cantilever nanoprobe operated at contact mode and a positive photoresist, various nanopatterns are produced on thin photoresist layer coated on the silicon substrate. The size and shape variations of thereby produced patterns are investigated using atomic force microscope to determine their uniformity and reproducibility. It is demonstrated that the NSOL-produced photo-resist nanomasks can be successfully applied for silicon pattern transfer by fabricating a silicon nanochannel array.     

Recent Progress in Simple and Cost-Effective Top-Down Lithography for ≈10 nm Scale Nanopatterns: From Edge Lithography to Secondary Sputtering Lithography

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.     

High speed fabrication of aluminum nanostructures with 10 nm spatial resolution by electrochemical replication

A high fidelity electrochemical replication technique for the rapid fabrication of Al nanostructures with 10?nm lateral resolution has been successfully demonstrated. Aluminum is electrodeposited onto a lithographically patterned Si master using a non-aqueous organic hydride bath of aluminum chloride and lithium aluminum hydride at room temperature. Chemical pretreatment of the Si surface allows a clean detachment of the replicated Al foil from the master, permitting its repetitive use for mass replication. This high throughput technique opens up new possibilities in the fabrication of Al-related nanostructures, including the growth of long range ordered anodic alumina nanochannel arrays.     

Hierarchical structural nanopore arrays fabricated by pre-patterning aluminum using nanosphere lithography

A highly ordered and hierarchical structural nanopore array is fabricated via anodizing a pre-patterned aluminum foil under an optimized voltage. A pre-patterned hexagonal nanoindentation array on an aluminum substrate is prepared via the nanosphere lithography method. This pattern leads to an elaborate nanochannel structure with seven nanopores in each nanoindentation after anodization treatment. The structure achieved in our study is new, interesting, and likely to be applied in photonic devices.     

Metal nanostructures fabricated by selective metal nanoscale etch method

A new method for fabricating metal nanostructures, called ‘the selective metal nanoscale etch method (SMNEM)’, was developed. The SMNEM consists of a galvanic displacement and selective etching process. The process was found to be simple and produced a uniform surface with a self-controlled etch rate of 32.2 ± 2.1 nm per cycle at a temperature and immersion time of 75°C and 3 min, respectively. Since it is a wet chemical process, SMNEM provides high throughput and low temperature etching which is compatible with conventional semiconductor processes. Various metal nanostructures, such as nanostairs, nanogratings, and nanowires were produced using SMNEM.     

2A96铝合金表面阳极氧化及性能研究

针对铝合金表面极易氧化生成结构疏松、耐腐蚀性差的氧化膜问题,利用阳极氧化法对2A96铝合金表面进行防腐蚀处理。通过改变阳极氧化实验中的氧化电压,在2A96铝合金表面制备不同的阳极氧化膜;利用金相显微镜观察各个阳极氧化膜的表面形貌、测厚仪测量其厚度、显微硬度计测定其硬度、点滴实验获取其点滴时间、电化学工作站获取其极化曲线和交流阻抗谱,进而对阳极氧化膜的耐腐蚀性进行研究。结果表明,在所测电压范围(8～16 V)内,随着电压的升高,阳极氧化膜的厚度、硬度、点滴时间也逐渐增加,耐腐蚀性能也随之增强。2A96铝合金经过表面阳极化处理后,其性能显著提高。     

用于表面编码器的正弦波栅格的热模压制

本文介绍了在多自由度纳米定位中,作为表面编码器测量基准的正弦波栅格的复制方法．该栅格表面的形貌为空间正弦波,即沿x和y方向均为波长100μm,振幅100nm的正弦波．这种栅格表面的大小为几十微米至几百微米．在安装了快速刀具伺服机构的金刚石车床上,制成了铝基栅格表面．该加工系统的优点是能够以高精度形成被加工表面,但另一方面,由于是在大面积内形成微观表面,故加工时间较长．为了实现快速制作,进行了基于基表面的复制,栅格表面的复制采取了热模压制法,在高分子薄膜上进行了实验．     

Prozess zur Anodisierung von Aluminiumbändern mit hoher elektrischer Durchschlagsspannung

Process for anodizing of aluminum stripes with high electrical breakdown voltage The Aim of the research was to develop an anodizing process for generating a high breakdown voltage on aluminum stripes in the shortest processing time possible. In order to vary process parameters in a wide range, a flexible discontinuous anodizing laboratory device was designed in cooperation with Steinert Elektromagnetbau GmbH Köln. By means of the liquid contact method, conditions equal to non‐solid contact anodizing of aluminum stripes in continuous laboratory devices were simulated. The research was focused on the development of the current pulse shape. The results show that the highest possible breakdown voltages can be achieved in a short processing time using suitable electrical parameters (current pulse shape) and the appropriate post‐treatment. The films generated by the new technology (current pulse shape referred to as “TUCAL”) reveal a higher pore density than conventional layers. This results in a higher ductility (less tendency for cracking).     

Variation of nanopore diameter along porous anodic alumina channels by multi-step anodization

In order to form tapered nanocapillaries, we investigated a method to vary the nanopore diameter along the porous anodic alumina (PAA) channels using multi-step anodization. By anodizing the aluminum in either single acid (H3PO4) or multi-acid (H2SO4, oxalic acid and H3PO4) with increasing or decreasing voltage, the diameter of the nanopore along the PAA channel can be varied systematically corresponding to the applied voltages. The pore size along the channel can be enlarged or shrunken in the range of 20 nm to 200 nm. Structural engineering of the template along the film growth direction can be achieved by deliberately designing a suitable voltage and electrolyte together with anodization time.     

阳极氧化工艺对纤维-铝合金层板力学性能的影响

通过改变铝合金表面阳极氧化工艺参数, 研究了阳极氧化电压和时间对玻璃纤维-铝合金(GLARE)层板抗拉强度和层间剪切强度的影响。通过SEM观察了铝合金表面Al₂O₃多孔膜和层板断面形貌, 分析了铝合金/树脂胶接界面对层板力学性能的影响。结果表明, 阳极氧化电压为20 V时, GLARE层板抗拉强度和层间剪切强度随着阳极氧化时间延长而增大, 在20 min时出现最大值, 继续延长阳极氧化时间, 层板强度随之下降; 阳极氧化时间为20 min时, GLARE层板抗拉强度和层间剪切强度随着阳极氧化电压增大而增大, 在20 V时出现最大值, 继续增大电压, 强度随之下降。     

Effect of process parameters on growth rate and diameter of nano-porous alumina templates

Anodic aluminium oxide (AAO) template with hexagonal shaped nano-pores with high aspect ratio was fabricated by two-step anodization processes from high purity aluminium foil. It was observed that pore dimensions were affected by anodizing voltage, electrolyte temperature and the duration of anodization time. The vertical growth rate of the pores (10?C250?nm/min) was found to vary exponentially with anodizing voltage; however, it exhibits linear increment with the electrolyte temperature. The measured pore diameter (50?C130?nm) shows a linear variation with anodizing voltage. The bottom barrier oxide layer was etched out by pore widening treatment to obtain through holes.     

On the growth sequence of highly ordered nanoporous anodic aluminium oxide

Anodic aluminium oxide films were fabricated by well known two-step anodizing process in oxalic acid electrolyte. The ordering characteristics (ordered pore domains, average pore diameter size and through-pore arrangement) of anodic aluminium oxide films, obtained in different growth sequences, were identified by microscopic analysis such as ex situ contact-mode atomic force microcopy and scanning electron microscopy. Flattened areas in which some pits are seen mostly cover the electropolished surface of aluminium. Single anodizing of aluminium produces a broad distribution of nanopore size, whereas induces a highly ordered hemispherical pattern, which plays the ordered nucleation sites for the second anodizing step. Moreover, a quasi-linear growth behavior exists for the ordered domain growth versus the duration of first step anodizing. The through-pore arrangement of ideally grown membranes is not influenced by increasing the duration of second step anodizing.     

Resistless Nanoimprinting in Metal for Plasmonic Nanostructures

Metal nanostructures are the main building blocks of metamaterials and plasmonics which show many extraordinary properties not existing in nature. A simple and widely applicable method that can directly pattern metals with silicon molds without the need of resists, using pressures of <4 MPa and temperatures of 25–150 °C is reported. Three‐dimensional structures with smooth and vertical sidewalls, down to sub‐10 nm resolution, are generated in silver and gold films in a single patterning step. Using this nanopatterning scheme, large‐scale vivid images through extraordinary optical transmission and strong surface‐enhanced Raman scattering substrates are realized. Resistless nanoimprinting in metal (RNIM) is a new class of metal patterning that allows plasmonic nanostructures to be fabricated quickly, repeatedly, and at a low‐cost.     

Surface-enhanced Raman scattering substrate of silver nanoparticles depositing on AAO template fabricated by magnetron sputtering

In this report, we describe a fabrication process of low-cost and highly sensitive SERS substrates by using a simple anodizing setup and a low-energy magnetron sputtering method. The structure of the SERS substrates consists of silver nanoparticles deposited on a layer of anodic aluminum oxide (AAO) template. The fabricated SERS substrates are investigated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), and a confocal Raman spectroscope. We have verified from the surface morphology that the fabricated SERS substrates consist of high-density round-shape silver nanoparticles where their size distribution ranges from 10 to 30 nm on the top and the bottom of nanopores. The surface-enhanced Raman scattering activities of these nanostructures are demonstrated using methylene blue (MB) as probing molecules. The detection limit of 10⁻⁸ M can be achieved from this SERS substrate.