采用水基原子层沉积工艺在石墨烯上沉积Al2O3介质薄膜研究

采用水基原子层沉积(H2O-based ALD)方法在石墨烯上直接生长Al2O3介质薄膜,研究了Al2O3成核机理.原子力显微镜(AFM)对Al2O3薄膜微观形态分析表明,沉积温度决定着Al2O3在石墨烯表面的成核生长情况,物理吸附在石墨烯表面的水分子是Al2O3成核的关键,物理吸附水分子的均匀性直接影响Al2O3薄膜的均匀性.在适当的温度窗口(100～130℃),Al2O3可以均匀沉积在石墨烯上,AFM测得Al2O3薄膜表面均方根粗糙度(RMS)为0.26 nm,X射线光电子能谱(XPS)表面分析与元素深度剖析表明,120℃下在石墨烯表面沉积的Al2O3薄膜中O和Al元素的含量比约为1.5.拉曼光谱分析表明,采用H2O-based ALD工艺沉积栅介质薄膜不会降低石墨烯晶体质量.     

Atomic layer deposition ultra-barriers for electronic applications-strategies and implementation

We show that Al2O3 thin films, grown by atomic layer deposition (ALD) on polyester, are ultrabarriers with moisture permeation <10(-5) g-H2O/m2-day, as determined after aging for more than three years. We present evidence that the mechanism for gas permeation in ALD Al2O3 films is not due to pinholes, but that the onset of permeation occurs abruptly, analogous to electrical breakdown in oxide thin films. We show that the permeation onset time increases for thicker Al2O3 films and higher ALD process temperature, for which the hydrogen defect concentration in Al2O3 films is less. Further, we show that mild plasma treatment of the polyester, prior to ALD deposition of Al2O3, makes the surface more hydrophilic and reduces moisture permeation compared to an untreated surface. Similarly, ALD deposition on the bare or non-slip side of the polyester film is preferred for low permeation.     

Scalable production of ultra small TiO2 nano crystal/activated carbon composites by atomic layer deposition for efficient removal of organic pollutants

A high surface area photo-catalytic composite material is synthesized by depositing thin films of titanium dioxide (TiO₂) on activated carbon (AC) particles using atomic layer deposition (ALD). A rotary ALD reactor is developed for scalable fabrication of powder and grams of the catalyst is prepared in each batch. The processes of TiO₂ ALD are monitored by mass spectrometry. Saturated ALD surface reactions are confirmed so that the entire surface of the AC support is covered by conformal coatings of TiO₂. For composites fabricated by 3 or more ALD cycles of TiO₂, the amorphous oxide layers can be converted to crystalline films by high temperature annealing. The as-prepared TiO₂/AC composites are highly reactive in photo-catalyzed degradation of methyl orange. The excellent catalytic performance is attributed to the abundant and uniformly dispersed active phase, formation of very active ultra small (<5 nm) TiO₂ crystals, and easy accessibility of the active sites.     

Conformal nanocoating of zirconia nanoparticles by atomic layer deposition in a fluidized bed reactor

Primary zirconia nanoparticles were conformally coated with alumina ultrathin films using atomic layer deposition (ALD) in a fluidized bed reactor. Alternating doses of trimethylaluminium and water vapour were performed to deposit Al(2)O(3) nanolayers on the surface of 26?nm zirconia nanoparticles. Transmission Fourier transform infrared spectroscopy was performed ex situ. Bulk Al(2)O(3) vibrational modes were observed for coated particles after 50 and 70?cycles. Coated nanoparticles were also examined with transmission electron microscopy, high-resolution field emission scanning electron microscopy and energy dispersive spectroscopy. Analysis revealed highly conformal and uniform alumina nanofilms throughout the surface of zirconia nanoparticles. The particle size distribution and surface area of the nanoparticles are not affected by the coating process. Primary nanoparticles are coated individually despite their high aggregation tendency during fluidization. The dynamic aggregation behaviour of zirconia nanoparticles in the fluidized bed plays a key role in the individual coating of nanoparticles.     

Electroplating to visualize defects in Al2O3 thin films grown using atomic layer deposition

Thin films grown using atomic layer deposition (ALD) are known for being continuous and nearly pinhole-free. These characteristics enable ALD films to be important in many applications such as gas or copper diffusion barriers, gate dielectrics, surface modification and functionalization layers. Few methods have been demonstrated to characterize defects in ALD films. In this study, a method to render the defects visible in Al₂O₃ ALD thin films on conductive substrates has been developed by growing copper bumps locally at the defect sites using electroplating. The electroplated copper can be easily observed or inspected using conventional optical- or electron-microscopy. Using this approach, the defect density in Al₂O₃ ALD thin films grown on nickel substrates has been shown to be as low as 38 /cm².     

Surface modification of organic powders for enhanced rheology via atomic layer deposition

Some organic additive manufacturing feedstocks can be cohesive and tend to agglomerate in suspensions, which can lead to significant challenges in formulating solids-loaded fluids, like those used in many additive manufacturing processes. By depositing an ultra-thin, layer of a second material conformally with the surface of the feedstock powder, Atomic Layer Deposition (ALD) can be used to uniquely modify the surface and, thereby, cohesion of the powder material without changing the properties of the bulk material. This paper demonstrates low temperature (<115 °C), ALD of aluminum oxide on temperature-sensitive materials: first, on polyimide thin film flats, then, on melamine and nylon organic powder feedstocks with the goal of improving their powder rheology. The process produced amorphous aluminum oxide-hydroxide coatings that are both uniform and conformal to the powder’s surface. Aluminum oxide coatings on the nylon powders did not show a significant change in the flow properties of the powder, given the already low cohesivity of nylon. In contrast, the highly cohesive melamine powders exhibited significant improvements in flowability after being coated with a layer as thin as 20 nm, due to a reduction in inter-particle cohesivity. The basic flowability decreased from 199 to 185 mJ and the specific energy increased from 4.95 to 6.39 mJ/g.     

Using fence post designs to speed the atomic layer deposition of optical thin films

Atomic layer deposition (ALD) at this time is much slower than conventional optical thin-film deposition techniques. A more rapid ALD process for SiO(2) has been developed than for other ALD materials. A fence post design for optical thin films has thin layers of high-index posts standing above a broad low-index ground. If a design for ALD can be predominantly composed of SiO(2) layers with thin high-index layers, the deposition times can be correspondingly shortened, and it is shown that the required performance can still be nearly that of more conventional designs with high- and low-index layers of equal thickness. This combination makes the ALD benefits of conformal coating and precise thickness control more practical for optical thin-film applications.     

An overview of highly porous oxide films with tunable thickness prepared by molecular layer deposition

This paper is a short review about the principle, preparation, and applications of ultra-thin oxide films prepared by molecular layer deposition (MLD). Porous oxide films, with well-defined porous structures and precisely controlled thicknesses down to several angstroms, can be prepared from dense organic/inorganic hybrid polymer films grown by MLD. The organic constituents in the film can be removed either by calcination at elevated temperatures or mild water etching at room temperature. Because of the layer-by-layer growth process for MLD, the deposited polymer films have regular structures and the removal of organic components from MLD polymer films produces uniform interconnected highly porous structures with a high surface area. For example, porous aluminum oxide films prepared by such a method have both micropores and mesopores with a BET surface area as high as 1250 m²/g. Examples of the versatility of the technique for fabrication of novel functional materials for various applications are discussed, including thermally stable, highly selective metal nanoparticle catalysts, defect-free inorganic membranes for gas separation, and photocatalytic layers prepared from titanium alkoxide MLD films.     

From Precursor Chemistry to Gas Sensors: Plasma‐Enhanced Atomic Layer Deposition Process Engineering for Zinc Oxide Layers from a Nonpyrophoric Zinc Precursor for Gas Barrier and Sensor Applications

The identification of bis‐3‐(N,N‐dimethylamino)propyl zinc ([Zn(DMP)₂], BDMPZ) as a safe and potential alternative to the highly pyrophoric diethyl zinc (DEZ) as atomic layer deposition (ALD) precursor for ZnO thin films is reported. Owing to the intramolecular stabilization, BDMPZ is a thermally stable, volatile, nonpyrophoric solid compound, however, it possesses a high reactivity due to the presence of Zn‐C and Zn‐N bonds in this complex. Employing this precursor, a new oxygen plasma enhanced (PE)ALD process in the deposition temperature range of 60 and 160 °C is developed. The resulting ZnO thin films are uniform, smooth, stoichiometric, and highly transparent. The deposition on polyethylene terephthalate (PET) at 60 °C results in dense and compact ZnO layers for a thickness as low as 7.5 nm with encouraging oxygen transmission rates (OTR) compared to the bare PET substrates. As a representative application of the ZnO layers, the gas sensing properties are investigated. A high response toward NO₂ is observed without cross‐sensitivities against NH₃ and CO. Thus, the new PEALD process employing BDMPZ has the potential to be a safe substitute to the commonly used DEZ processes.     

Reduction of titanium and other metal oxides using electrodeoxidation

Abstract

Many reactive and refractory metals are currently produced industrially by reducing their compounds, including oxides, using a more reactive metal. In some cases, where there is substantial oxygen solubility in the metal, the oxygen is first removed by carbochlorination followed by reduction. Titanium and zirconium are made by reduction of the volatile tetrachlorides by magnesium. The processes consist essentially of two reduction steps: reducing magnesium chloride to magnesium metal and then reduction of the metal compound; this makes the overall reduction process relatively expensive. Electrodeoxidation is very simple in that the oxide to be reduced is rendered cathodic in molten alkaline earth chloride. By applying a voltage below the decomposition potential of the salt, it has been found that ionisation of oxygen is the dominant cathode reaction, rather than alkaline earth metal deposition. In the laboratory, this technique has been applied to reduce a large number of metal oxides to the metals, including titanium, zirconium, chromium, niobium, tantalum, uranium and nickel. Furthermore, when mixed oxides are used as the cathode, alloys or intermetallic compounds of uniform composition are obtained. This may offer advantages over conventional technology for those alloys that are difficult to prepare at present, owing to differences in either density or vapour pressure.     

Atomic Layer Deposition on Dispersed Materials in Liquid Phase by Stoichiometrically Limited Injections

Atomic layer deposition (ALD) is a well‐established vapor‐phase technique for depositing thin films with high conformality and atomically precise control over thickness. Its industrial development has been largely confined to wafers and low‐surface‐area materials because deposition on high‐surface‐area materials and powders remains extremely challenging. Challenges with such materials include long deposition times, extensive purging cycles, and requirements for large excesses of precursors and expensive low‐pressure equipment. Here, a simple solution‐phase deposition process based on subsequent injections of stoichiometric quantities of precursor is performed using common laboratory synthesis equipment. Precisely measured precursor stoichiometries avoid any unwanted reactions in solution and ensure layer‐by‐layer growth with the same precision as gas‐phase ALD, without any excess precursor or purging required. Identical coating qualities are achieved when comparing this technique to Al₂O₃ deposition by fluidized‐bed reactor ALD (FBR‐ALD). The process is easily scaled up to coat >150 g of material using the same inexpensive laboratory glassware without any loss in coating quality. This technique is extended to sulfides and phosphates and can achieve coatings that are not possible using classic gas‐phase ALD, including the deposition of phosphates with inexpensive but nonvolatile phosphoric acid.     

Atomic layer deposition (ALD): A versatile technique for plasmonics and nanobiotechnology

While atomic layer deposition (ALD) has been used for many years as an industrial manufacturing method for microprocessors and displays, this versatile technique is finding increased use in the emerging fields of plasmonics and nanobiotechnology. In particular, ALD coatings can modify metallic surfaces to tune their optical and plasmonic properties, to protect them against unwanted oxidation and contamination, or to create biocompatible surfaces. Furthermore, ALD is unique among thin-film deposition techniques in its ability to meet the processing demands for engineering nanoplasmonic devices, offering conformal deposition of dense and ultra-thin films on high-aspect-ratio nanostructures at temperatures below 100 °C. In this review, we present key features of ALD and describe how it could benefit future applications in plasmonics, nanosciences, and biotechnology.     

Effect of catalyst for nickel films for NiSi formation with improved interface roughness

Iodine is an effective catalyst to obtain homogeneous and smooth metal films with good interface properties. We adopted an iodine catalyst during the nickel film deposition by using atomic layer deposition (ALD) with bis(1-dimethylamino-2-methyl-2-butoxide)nickel [Ni(dmamb)₂] precursor and hydrogen reactant gas. The effect of iodine catalyst to nickel nucleation process was studied. The deposited films were silicided by rapid thermal process (RTP) which was performed by varying temperature from 400 °C to 900 °C in nitrogen ambient. The crystalline properties of nickel and nickel silicide films were examined by X-ray diffractometer (XRD) with various deposition temperatures. The interface properties and the surface morphology of nickel silicide films were studied by using Auger electron spectroscopy (AES) depth profile analyses and scanning electron microscopy (SEM). The experimental results showed that the iodine-catalyzed silicide film, which have a clean and smooth interface, exhibit lower resistivity, and lower leakage current density compared to that of non iodine-catalyzed films in implemented n⁺/p junction diode.     

Ultrasonic assisted fabrication of particle reinforced bonds joining aluminum metal matrix composites

This paper presents a method of producing uniform particle strengthened bonds between pieces of aluminum metal matrix composite (Al-MMCs), of strength equal to that of the substrate material. SiC particle reinforced Zn-based filler metals were fabricated by mechanical stir casting and ultrasonic treatment, and then used to join pieces of SiC_p/A356 composite with the aid of ultrasonic vibration. The filler metals made by mechanical stirring were porous and contained many particle clusters. Ultrasonic vibration was used to disperse the agglomerates and prevent further coagulation of SiC particles during joining, but the method failed to eliminate the porosity, resulting in a highly porous bond. The filler metal treated by ultrasonic vibration was free of defects and produced a non-porous bond strengthened with uniform particles between pieces of SiC_p/A356 composite. The presence of surface oxide films at the bonding interface significantly degraded the performance of SiC particle reinforced bond. Removal of this oxide film by at least 4 s of ultrasonic vibration significantly increased the bond strength, reaching a value equal to that of the substrate metal.     

光催化分解水制氢体系助催化剂研究进展

煤、石油、天然气等不可再生能源的消耗导致环境污染日益严重,开发和使用清洁的可再生能源迫在眉睫。利用太阳能光催化分解水制氢被认为是解决化石能源紧缺和环境污染问题的有效途径之一。光催化分解水制氢体系非常复杂,助催化剂是影响催化剂光催化效率的一个关键因素,它的引入可以有效提高催化剂的光催化活性和氢气产生速率,因此,开发廉价高效的助催化剂已逐渐成为本领域的研究热点。本文结合光催化分解水制氢原理,简要介绍了助催化剂的作用,对近年来光催化分解水产氢助催化剂的种类和研究内容进行了总结,分析和讨论了几类重要助催化剂的特点及作用机理,并对助催化剂的发展进行了展望,以期为新型高效光催化制氢材料的设计提供参考。     

In situ gas phase measurements during metal alkylamide atomic layer deposition

Metal alkylamide compounds, such as tetrakis(ethylmethylamido) hafnium (TEMAH), represent a technologically important class of metalorganic precursors for the deposition of metal oxides and metal nitrides via atomic layer deposition (ALD) or chemical vapor deposition. The development of in situ diagnostics for processes involving these compounds could be beneficial in, e.g., developing deposition recipes and validating equipment-scale simulations. This report describes the performance of the combination of two techniques for the simultaneous, rapid measurement of the three major gas phase species during hafnium oxide thermal ALD using TEMAH and water: TEMAH, water, and methylethyl amine (MEA), the only major reaction by-product. For measurement of TEMAH and MEA, direct absorption methods based on a broadband infrared source with different mid-IR bandpass filters and utilizing amplitude modulation and synchronous detection were developed. For the measurement of water, wavelength modulation spectroscopy utilizing a near-IR distributed feedback diode laser was used. Despite the relatively simple reactor geometry employed here (a flow tube), differences were easily observed in the time-dependent species distributions in 300 mL/min of a helium carrier gas and in 1000 mL/min of a nitrogen carrier gas. The degree of TEMAH entrainment was lower in 300 mL/min of helium compared to that in 1000 mL/min of nitrogen. The capability to obtain detailed time-dependent species concentrations during ALD could potentially allow for the selection of carrier gas composition and flow rates that would minimize parasitic wall reactions. However, when nitrogen was employed at the higher flow rates, various flow effects were observed that, if detrimental to a deposition process, would effectively limit the upper range of useful flow rates.     

Ultra thin nickel transparent electrodes

Transparent electrodes made of ultra thin metals have recently been demonstrated with performances comparable to those offered by transparent conductive oxides (TCOs), which are traditionally used in applications such as photovoltaic cells, light emitting devices, photodetectors and electro-optical modulators. In this work we report highly uniform, optically transparent and electrically conductive nickel films. Their good performance, combined with low cost and simplicity in processing, make ultra thin Ni films highly competitive, even with respect to the latest developments in TCO technology. Nickel films can be easily incorporated into an industrial process flow and could therefore be an attractive alternative to TCOs in many industrial applications.     

High‐Quality,Ultraconformal Aluminum‐Doped Zinc Oxide Nanoplasmonic and Hyperbolic Metamaterials

Aluminum‐doped zinc oxide (AZO) is a tunable low‐loss plasmonic material capable of supporting dopant concentrations high enough to operate at telecommunication wavelengths. Due to its ultrahigh conformality and compatibility with semiconductor processing, atomic layer deposition (ALD) is a powerful tool for many plasmonic applications. However, despite many attempts, high‐quality AZO with a plasma frequency below 1550 nm has not yet been realized by ALD. Here a simple procedure is devised to tune the optical constants of AZO and enable plasmonic activity at 1550 nm with low loss. The highly conformal nature of ALD is also exploited to coat silicon nanopillars to create localized surface plasmon resonances that are tunable by adjusting the aluminum concentration, thermal conditions, and the use of a ZnO buffer layer. The high‐quality AZO is then used to make a layered AZO/ZnO structure that displays negative refraction in the telecommunication wavelength region due to hyperbolic dispersion. Finally, a novel synthetic scheme is demonstrated to create AZO embedded nanowires in ZnO, which also exhibits hyperbolic dispersion.     

Surface engineering of synthetic nanopores by atomic layer deposition and their applications

In the past decade, nanopores have been developed extensively for various potential applications, and their performance greatly depends on the surface properties of the nanopores. Atomic layer deposition （ALD） is a new technology for depositing thin films, which has been rapidly developed from a niche technology to an established method. ALD films can cover the surface in confined regions even in nanoscale conformally, thus it is proved to be a powerful tool to modify the surface of the synthetic nanopores and also to fabricate complex nanopores. This review gives a brief introduction on nanopore synthesis and ALD fundamental knowledge, and then focuses on the various aspects of synthetic nanopores processing by ALD and their applications, including single-molecule sensing, nanofiuidic devices, nanostructure fabrication and other applications.