Integration of a carbon nanotube based electrode in silicon microtechnology to fabricate electrochemical transducers

An original approach was developed and validated for the fabrication of a carbon nanotube (CNT) electrode synthesized directly onto a carbon buffer thin film deposited on a highly doped monocrystalline silicon surface. The buffer layer of amorphous carbon thin film was deposited by physical vapour deposition on the silicon substrate before CNT synthesis. For this purpose, nickel was deposited on the carbon buffer layer by an electrochemical procedure and used as a catalyst for the CNT growth. The CNT synthesis was achieved by plasma enhanced chemical vapour deposition (PECVD) in an electron cyclotron resonance (ECR) plasma chamber using a C(2)H(2)/NH(3) gas mixture. In order to evaluate the electrochemical behaviour of the CNT-based electrode, the carbon layer and the silicon/carbon interface were studied. The resulting buffer layer enhanced the electronic transport from the doped silicon to the CNTs. The electrode surface was studied by XPS and characterized by both SEM and TEM. The electrochemical response exhibited by the resulting electrodes modified with CNTs was also examined by cyclic voltammetry. The whole process was found to be compatible with silicon microtechnology and could be envisaged for the direct integration of microsensors on silicon chips.     

Y-junction multibranched carbon nanofibers

Multibranched carbon nanofiber (CNF) is produced by a thermal chemical vapor deposition method using camphor as precursor. Nickel and cobalt catalyst was deposited on silicon substrate by e-beam evaporation and used as substrate for the growth of carbon nanomaterials. Branched carbon nanofibers were grown on the nickel thin film at 900 degrees C, whereas spherical carbon beads formed on the cobalt thin film. These fibers followed base growth mechanism devoid of any catalyst particle at the tip of fibers.     

Preparation and characterization of nanostructured ZrO2 coatings on dense and porous substrates

Nanostructured ZrO₂ coatings are prepared on both dense and porous substrates by wet-chemical deposition of non-agglomerated 5 nm precursor particle dispersions, followed by thermal processing. The precursor particle dispersions are made by modified emulsion precipitation and a purification treatment to remove reaction products and additives. The coatings are formed by depositing the precursor nanoparticle dispersion directly onto the substrate, followed by drying and heating at 600 °C. Scanning electron microscopy and cross-sectional transmission electron microscopy observations of the heat-treated coatings indicate that the ZrO₂ coating on dense Si wafer substrate has a homogeneous, dense particle packing structure with shallow meniscus-shaped depressions in the surface, and microcracks below the meniscus surface. On the other hand, coatings formed on a meso-porous γ-alumina membrane substrate are free of defects, but with a lower packing density. The mechanism of the substrate effect on the particle packing behavior and defect formation during coating deposition is discussed. It is expected that by using a thin porous substrate with reduced capillary force, a defect-free, homogenously dense-packed coating structure can be achieved.     

Study of the growth of rhodium particles on different substrates

We have investigated the growth of small supported rhodium particles on different substrates (mica, Al₂O₃, NaCl). The particles were deposited in a vacuum from a special source permitting a low evaporation rate. The particle size, density and crystallographic structure dependencies on mean deposit thickness, deposition rate and substrate temperature during the deposition were studied by transmission electron microscopy and diffraction (TEM and TED). The results showed that it is possible to prepare a model Rh catalyst with a well-defined particle population by vacuum vapour deposition. These catalysts form relatively stable systems with respect to the thermal treatment. It was observed that the particle density, the mean size and the size dispersion of Rh particles are controlled by either atom diffusion or by particle migration on the substrate. The diffusion of atoms and clusters increases with the substrate temperature and the growth takes place also by particle coalescence.     

Transparente und leitfähige Veredelung von Kunststoffoberflächen

Deposition Techniques for Transparent Conducting Thin‐Films on Glass and Polymer Substrates We report on thin films deposited at atmospheric pressures on glass and polymer substrates with various techniques. The introduced thin‐film materials show intrinsic properties being suitable for different applications while maintaining the principle properties of the substrates themselves (e. g. shape. rigidity/flexibility, transparency). With the main focus on optical and electronic applications the properties of the deposited films can be adjusted by the choice of coating material (e. g. metal oxide, CNT), the film's shape (compact, particulate) and the deposition process itself. We compare deposition and properties of different TCO‐materials with CNT‐based thin film techniques and demonstrate approaches for the integration of these processes in production lines.     

锌微晶辅助碳纳米管图案化

利用锌微晶沸点较低易于蒸发以及形态丰富多变的特点,在微米尺度的锌晶粒介入下采用两种方式实现碳纳米管的组装.方法一:先蒸发得到一定尺度的锌微晶,然后以其为牺牲模板基于化学气相沉积生长技术实现碳纳米管的原位组装;方法二:与方法一的工艺过程相反,先在SiO2基片上气相沉积获得定向碳纳米管膜,然后以其为基板蒸发沉积锌微米晶对生长后的碳纳米管膜进行形貌调控和组装.结果表明,尽管两种组装方式的过程和原理不同,但都可获得碳纳米管的组装图案,且过程简单可控.这一技术可为碳纳米管的组装提供新途径.     

Preconcentration of volatile organics on self-assembled, carbon nanotubes in a microtrap

This paper reports the self-assembly of carbon nanotubes (CNTs) on the inside wall of a steel capillary to fabricate a microtrap for the adsorption/desorption of trace organics. The microtrap functioned as a nanoconcentrator and an injector for gas chromatography (GC). The CNTs were deposited as a thin film by catalytic chemical vapor deposition from either CO or C2H4 as the precursor. The sorbent film synthesized from C2H4-CVD (CVD = chemical vapor deposition) had higher CNT density and thus was a stronger sorbent. In general, the CNT microtraps showed high-capacity adsorption and fast quantitative desorption, and the process showed excellent precision. This study demonstrates that CNT films can be deposited quite easily in a steel capillary for use in different analytical applications, and CNT films can perform as efficiently as packed-bed carbon sorbents.     

Clean carbon nanotube field emitters aligned horizontally

Horizontally aligned carbon nanotube (CNT) field emitters, which strongly adhere to the substrate and show good field emission properties, were fabricated by electrophoresis deposition and fissure formation techniques. A thin film of CNTs was deposited on a substrate, by electrophoresis, from an aqueous mixture of CNT and detergent, and then the detergent was deposited also by electropholysis. CNTs with a clean surface were exposed in the fissures produced by firing. The field emission was increased significantly due to the additional deposition of the detergent. When the CNTs were cut by increasing the firing time, the field emission increased significantly, while their stability decreased considerably. Our method does not require any further treatment for field emission.     

Roll-to-roll plasma deposition machine for the production of tandem amorphous silicon alloy solar cells

A roll-to-roll plasma deposition machine for depositing multilayered amorphous alloys has been developed. The plasma deposition machine has multiple deposition areas and processes a stainless steel substrate 16 in wide continuously. Amorphous photovoltaic thin films (less than 1 μm thick) with a six-layer structure (p-i-n-p-i-n) are deposited continuously in a single pass onto a roll of stainless steel substrate 16 in wide and 1000 ft long. Mass production of low cost tandem solar cells utilizing roll-to-roll processes is now possible. A commercial plant utilizing this plasma deposition machine for manufacturing tandem amorphous silicon alloy solar cells is now in operation.     

Growth control of carbon nanotubes by plasma enhanced chemical vapor deposition

Plasma enhanced chemical vapor deposition (PECVD), which enables growth of vertically aligned carbon nanotubes (CNTs) directly onto a solid substrate, is considered to be a suitable method for preparing CNTs for nanoelectronics applications such as electron sources for field emission displays (FEDs). For these purposes, establishment of an efficient CNT growth process has been required. We have examined growth characteristics of CNTs using a radio frequency PECVD (RF-PECVD) method with the intention to develop a high efficiency process for CNT growth at a low enough temperature suitable for nanoelectronics applications. Here we report an effect of pretreatment of the catalyst thin film that plays an important role in CNT growth using RF-PECVD. Results of this study show that uniform formation of fine catalyst nanoparticles on the substrate is important for the efficient CNT growth.     

Electrochemical characterization of carbon nanotube forests grown on copper foil using transition metal catalysts

Growth of vertical, multiwalled carbon nanotubes (CNTs) on bulk copper foil substrates can be achieved by sputtering either Ni or Inconel thin films on Cu substrates followed by thermal chemical vapor deposition using a xylene and ferrocene mixture. During CVD growth, Fe nanoparticles from the ferrocene act as a vapor phase delivered catalyst in addition to the transition metal thin film, which breaks up into islands. Both the thin film and iron are needed for dense and uniform growth of CNTs on the copper substrates. The benefits of this relatively simple and cost effective method of directly integrating CNTs with highly conductive copper substrates are the resulting high density of nanotubes that do not require the use of additional binders and the potential for low contact resistance between the nanotubes and the substrate. This method is therefore of interest for charge storage applications such as double layer capacitors. Inconel thin films in conjunction with Fe from ferrocene appear to work better in comparison to Ni thin films in terms of CNT density and charge storage capability. We report here the power density and specific capacitance values of the double layer capacitors developed from the CNTs grown directly on copper substrates.     

Selective growth of carbon nanotubes using catalyst poisoning and geometric trench

This work suggests catalyst poisoning and geometric patterned approaches to selectively grow multiwall carbon nanotubes. Ferromagnetic particles as a catalyst for CNTs growth vanish when they are deposited over an aluminum thin film. Additionally, geometric features, such as trenches or cavities, are revealed to be capable of selectively ceasing the growth of CNTs even though catalytic thin films were covered on entire samples by an atmospheric thermal chemical vapor deposition technique.     

One-dimensional carbon and ZnO

Carbon nanotube (CNT) and one-dimensional ZnO are two of the most important nano materials for which continuous efforts are being made for the development of novel processes. In this paper we present new approaches for the growth of CNTs and ZnO nanorods. Through the selection of an appropriate catalyst, namely, Fe-Si thin film, aligned CNT can be obtained at a temperature as low as 370 °C using a conventional microwave plasma-enhanced chemical vapor deposition (MPCVD) technique. This is attributed to the fact that the addition of Si greatly enhances the carbon diffusion such that a fast reaction-controlled growth is obtained. Also, with the use of a decisive electroless copper layer deposited on Si or glass substrate, semi-aligned ZnO nanorods can be obtained at the room temperature. It was found that the residual stress in the electroless copper is the key to the formation of ZnO nanorods.     

Fabrication of carbon nanoflakes by RF sputtering for field emission applications

In this paper, an ultra thin sheet-like carbon nanostructure, carbon nanoflake (CNF), has been effectively fabricated by RF sputtering on Si substrate without any catalyst or special substrate pre-treatment. The CNFs were chosen to be the field emission emitters because of their very sharp and thin edges which are potentially good electron field emission sites. The effect of deposition parameters such as substrate temperature, gas flow ratio and RF power on the field emission properties is discussed in detail. The sheet-like structures with thickness of about 10 nm or less stand on edge on the substrate and have a defective graphite structure. The field emission properties of the sample deposited at the optimum deposition conditions are turn-on field of 5.5 V/μm and current density of 1.4 mA/cm² at 11 V/μm. Considering the inexpensive manufacturing cost, lower synthesis temperature and ease of large-area preparation, the CNFs with low turn-on field deposited by RF sputtering might have a potential application in field emission devices.     

Structure–Property Relations in Carbon Nanotube Fibers by Downscaling Solution Processing

At the microscopic scale, carbon nanotubes (CNTs) combine impressive tensile strength and electrical conductivity; however, their macroscopic counterparts have not met expectations. The reasons are variously attributed to inherent CNT sample properties (diameter and helicity polydispersity, high defect density, insufficient length) and manufacturing shortcomings (inadequate ordering and packing), which can lead to poor transmission of stress and current. To efficiently investigate the disparity between microscopic and macroscopic properties, a new method is introduced for processing microgram quantities of CNTs into highly oriented and well‐packed fibers. CNTs are dissolved into chlorosulfonic acid and processed into aligned films; each film can be peeled and twisted into multiple discrete fibers. Fibers fabricated by this method and solution‐spinning are directly compared to determine the impact of alignment, twist, packing density, and length. Surprisingly, these discrete fibers can be twice as strong as their solution‐spun counterparts despite a lower degree of alignment. Strength appears to be more sensitive to internal twist and packing density, while fiber conductivity is essentially equivalent among the two sets of samples. Importantly, this rapid fiber manufacturing method uses three orders of magnitude less material than solution spinning, expanding the experimental parameter space and enabling the exploration of unique CNT sources.     

Cobalt Nanoparticle Arrays made by Templated Solid‐State Dewetting

Self‐assembled cobalt particle arrays are formed by annealing, which cause agglomeration (dewetting) of thin Co films on oxidized silicon substrates that are topographically prepatterned with an array of 200‐nm‐period pits. The Co nanoparticle size and uniformity are related to the initial film thickness, annealing temperature, and template geometry. One particle per 200‐nm‐period pit is formed from a 15‐nm film annealed at 850 °C; on a smooth substrate, the same annealing process forms particles with an average interparticle distance of 200 nm. Laser annealing enables templated dewetting of 5‐nm‐thick films to give one particle per pit. Although the as‐deposited films exhibit a mixture of hexagonal close‐packed and face‐centered cubic (fcc) phases, the ordered cobalt particles are predominantly twinned fcc crystals with weak magnetic anisotropy. Templated dewetting is shown to provide a method for forming arrays of nanoparticles with well‐controlled sizes and positions.     

Herstellung von Präzisionsschichten mittels Ionenstrahlsputtern

Precise thin film synthesis by ion beam sputter deposition Ion beam sputter deposition (IBSD) is a promising technique for the fabrication of high performance thin films because of the well defined and adjustable particle energies, which are rather high in comparison to other PVD techniques. Recent developments concerning long‐term stability and lateral uniformity of the ion beam sources strengthen the position of the IBSD technique in the field of precise thin film synthesis. Furthermore, IBSD offers a more independent choice of relevant deposition parameters like particle energy and flux, process gas pressure and deposition rate. In this paper we present our currently installed large area IBSD facility “IonSys 1600”, which was developed by Fraunhofer IWS Dresden and Roth & Rau company (Hohenstein‐Ernstthal). Substrate sizes of up to 200 mm (circular) or up to 500 mm length (rectangular) can be coated and multilayer stacks with up to six different materials are possible. Tailored 1‐ or 2‐dimensional film thickness distributions with deviations of < 0.1 % can be fabricated by a relative linear motion of the substrate holder above an aperture. In order to demonstrate the advantages of the IBSD technique especially for sophisticated materials and films with high requirements concerning purity, chemical composition or growth structure, several examples of deposited multilayers for various applications are presented.     

Growth and characterization of bamboo-shaped carbon nanotubes using nanocluster-assembled ZnO:Co thin films as catalyst

Bamboo-shaped carbon nanotubes (CNTs) had been successfully fabricated by a plasma enhanced chemical vapor deposition method, in which nanocluster-assembled ZnO:Co thin film was used as catalyst. It was found that bamboo-shaped CNTs were generally grown in a direction perpendicularly to the substrate surface with the tops of CNTs dominated by the droplet-like catalyst covered by the carbon layer. The diameter of CNTs was ranged from 20-50 nm. High resolution of TEM image showed that the typical CNT had a multi-walled structure with an inner core presented. The ordered graphite layers were inclined to an axis of CNT about 18 degrees and the interlayer space of a CNT was about 0.35 nm. Two peaks in Raman spectrum at 1586 cm(-1) and 1372 cm(-1) were identified as G-band and D-band for graphite, respectively. The results showed that catalyst based on ZnO:Co thin films could be used for the growth of CNTs with bamboo-shaped structure.     

衬底温度对碲化镉薄膜性质及太阳电池性能的影响

蒸汽输运法是制备高质量且大面积均匀的CdTe薄膜的一种优良的方法。采用自主研发的一套蒸汽输运沉积系统制备了CdTe多晶薄膜, 并研究了衬底温度对CdTe薄膜性质及太阳电池性能的影响。利用XRD、SEM、UV-Vis和Hall等测试手段研究了衬底温度对薄膜的结构、光学性质和电学性质的影响。结果表明, 蒸汽输运法制备的CdTe薄膜具有立方相结构, 且沿(111)方向高度择优。随着衬底温度的升高(520℃~640℃), CdTe薄膜的平均晶粒尺寸从2 μm增大到约6 μm, CdTe薄膜的载流子浓度也从1.93×10¹⁰ cm^-3提高到2.36×10¹³ cm^-3, 说明提高衬底温度能够降低CdTe薄膜的缺陷复合, 使薄膜的p型更强。实验进一步研究了衬底温度对CdTe薄膜太阳电池性能的影响, 结果表明适当提高衬底温度, 能够大幅度提高电池的效率、开路电压和填充因子, 但是过高的衬底温度又会降低电池的长波光谱响应, 导致电池转换效率的下降。经过参数优化, 在衬底温度为610℃、无背接触层小面积CdTe薄膜太阳电池的转换效率达到11.2%。     

Binder‐Free and Carbon‐Free 3D Porous Air Electrode for Li‐O2 Batteries with High Efficiency,High Capacity,and Long Life

Pt‐Gd alloy polycrystalline thin film is deposited on 3D nickel foam by pulsed laser deposition method serving as a whole binder/carbon‐free air electrode, showing great catalytic activity enhancement as an efficient bifunctional catalyst for the oxygen reduction and evolution reactions in lithium oxygen batteries. The porous structure can facilitate rapid O₂ and electrolyte diffusion, as well as forming a continuous conductive network throughout the whole energy conversion process. It shows a favorable cycle performance in the full discharge/charge model, owing to the high catalytic activity of the Pt‐Gd alloy composite and 3D porous nickel foam structure. Specially, excellent cycling performance under capacity limited mode is also demonstrated, in which the terminal discharge voltage is higher than 2.5 V and the terminal charge voltage is lower than 3.7 V after 100 cycles at a current density of 0.1 mA cm^?2. Therefore, this electrocatalyst is a promising bifunctional electrocatalyst for lithium oxygen batteries and this depositing high‐efficient electrocatalyst on porous substrate with polycrystalline thin film by pulsed laser deposition is also a promising technique in the future lithium oxygen batteries research.