Gas Sensing of NiO‐SCCNT Core–Shell Heterostructures: Optimization by Radial Modulation of the Hole‐Accumulation Layer

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al₂O₃ dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al₂O₃–SCCNT, Al₂O₃–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region.     

Gyroid‐Structured 3D ZnO Networks Made by Atomic Layer Deposition

3D continuous ZnO morphologies with characteristic feature sizes on the 10 nm length scale are attractive for electronic device manufacture. However, their synthesis remains a challenge because of the low crystallization temperature of ZnO. Here, we report a method for the robust and reliable synthesis of fully crystalline 3D mesoporous ZnO networks by means of atomic layer deposition (ALD) of ZnO into a self‐assembled block copolymer template. By carefully optimizing the processing conditions we are able to synthesize several‐micrometer‐thick layers of mesoporous ZnO networks with a strut width of 30 nm. Two 3D mesoporous morphologies are manufactured: a periodic gyroid structure and a random worm‐like morphology. Exploiting the ALD property to conformally coat complex surfaces of high aspect ratio, the channel network of a 3D continuous channel network of a self‐assembled block copolymer is replicated into ZnO. X‐ray photoemission spectroscopy and x‐ray diffraction measurements reveal that the chemical composition of the mesoporous structures is uniform and consists of wurtzite‐ZnO throughout the film. Scanning electron microscopy reveals an average pore dimension of 30 nm. The potential of this material for a hybrid photovoltaic application is demonstrated by the manufacture of a poly(3‐hexylthiophene)/ZnO solar cell.     

原子层沉积超薄氮化铝薄膜的椭圆偏振光谱法表征

采用原子层沉积(ALD)工艺在硅衬底上生长了35 nm以下不同厚度的超薄氮化铝(AlN)晶态薄膜。利用椭圆偏振光谱法在波长275~900 nm内测量并拟合薄膜的厚度及折射率和消光系数等光学参数。利用原子力显微镜(AFM)表征AlN晶粒尺寸随生长循环次数的变化,计算得到薄膜表面粗糙度并用于辅助椭偏模型拟合。针对ALD工艺特点建立合适的椭偏模型,可获得AlN超薄膜的生长速率为0.0535 nm/cycle,AlN超薄膜的折射率随着生长循环次数的增加而增大,并逐渐趋于稳定,薄膜厚度为6.88 nm时,其折射率为1.6535,薄膜厚度为33.01 nm时,其折射率为1.8731。该模型为超薄介质薄膜提供了稳定、可靠的椭圆偏振光谱法表征。     

热原子层沉积技术制备TiAlCN薄膜的特性

在Si和SiO2基底上,采用热原子层沉积技术,以四(二甲基氨基)钛(Ti(N (CH3)2)4)和三甲基铝(Al (CH3)3)为前驱体,制备TiAlCN薄膜.测试结果表明,随着基底温度的升高,膜层的沉积速率升高,电阻率降低,光学带隙由3.45 eV降低到2.00 eV,并在基底温度为300和350℃时出现了双吸收边;基底温度为350℃时,Al (CH3)3分解,使Al进入膜层与TiN和TiC形成TiAlN和TiAlC;膜层中TiN和TiC的形成,可以有效抑制膜层的自然氧化;基底温度为250和300℃时,薄膜为无定型结构,当基底温度为350℃时,有TiN晶体产生;膜层的表面粗糙度随着基底温度的升高先降低后升高,表面粗糙度的升高可能是因为在基底温度为350℃时前驱体材料的分解,使C-H键进入膜层所导致的.     

High‐Performance,Transparent Thin Film Hydrogen Gas Sensor Using 2D Electron Gas at Interface of Oxide Thin Film Heterostructure Grown by Atomic Layer Deposition

A high‐performance, transparent, and extremely thin (<15 nm) hydrogen (H₂) gas sensor is developed using 2D electron gas (2DEG) at the interface of an Al₂O₃/TiO₂ thin film heterostructure grown by atomic layer deposition (ALD), without using an epitaxial layer or a single crystalline substrate. Palladium nanoparticles (≈2 nm in thickness) are used on the surface of the Al₂O₃/TiO₂ thin film heterostructure to detect H₂. This extremely thin gas sensor can be fabricated on general substrates such as a quartz, enabling its practical application. Interestingly, the electron density of the Al₂O₃/TiO₂ thin film heterostructure can be tailored using ALD process temperature in contrast to 2DEG at the epitaxial interfaces of the oxide heterostructures such as LaAlO₃/SrTiO₃. This tunability provides the optimal electron density for H₂ detection. The Pd/Al₂O₃/TiO₂ sensor detects H₂ gas quickly with a short response time of <30 s at 300 K which outperforms conventional H₂ gas sensors, indicating that heating modules are not required for the rapid detection of H₂. A wide bandgap (>3.2 eV) with the extremely thin film thickness allows for a transparent sensor (transmittance of 83% in the visible spectrum) and this fabrication scheme enables the development of flexible gas sensors.     

Efficient Charge Injection in Organic Field‐Effect Transistors Enabled by Low‐Temperature Atomic Layer Deposition of Ultrathin VOx Interlayer

Charge injection at metal/organic interface is a critical issue for organic electronic devices in general as poor charge injection would cause high contact resistance and severely limit the performance of organic devices. In this work, a new approach is presented to enhance the charge injection by using atomic layer deposition (ALD) to prepare an ultrathin vanadium oxide (VO_x) layer as an efficient hole injection interlayer for organic field‐effect transistors (OFETs). Since organic materials are generally delicate, a gentle low‐temperature ALD process is necessary for compatibility. Therefore, a new low‐temperature ALD process is developed for VO_x at 50 °C using a highly volatile vanadium precursor of tetrakis(dimethylamino)vanadium and non‐oxidizing water as the oxygen source. The process is able to prepare highly smooth, uniform, and conformal VO_x thin films with precise control of film thickness. With this ALD process, it is further demonstrated that the ALD VO_x interlayer is able to remarkably reduce the interface contact resistance, and, therefore, significantly enhance the device performance of OFETs. Multiple combinations of the metal/VO_x/organic interface (i.e., Cu/VO_x/pentacene, Au/VO_x/pentacene, and Au/VO_x/BOPAnt) are examined, and the results uniformly show the effectiveness of reducing the contact resistance in all cases, which, therefore, highlights the broad promise of this ALD approach for organic devices applications in general.     

Polyphenol‐Sensitized Atomic Layer Deposition for Membrane Interface Hydrophilization

Improvements in energy–water systems will necessitate fabrication of high‐performance separation membranes. To this end, interface engineering is a powerful tool for tailoring properties, and atomic layer deposition (ALD) has recently emerged as a promising and versatile approach. However, most non‐polar polymeric membranes are not amenable to ALD processing due to the absence of nucleation sites. Here, a sensitization strategy for ALD‐coating is presented, illustrated by membrane interface hydrophilization. Facile dip‐coating with polyphenols effectively sensitizes hydrophobic polymer membranes to TiO₂ ALD coating. Tannic acid‐sensitized ALD‐coated membranes exhibit outstanding underwater crude oil repulsion and rigorous mechanical stability through bending and rinsing tests. As a result, these membranes demonstrate outstanding crude oil‐in‐water separation and reusability compared to untreated membranes or those treated with ALD without polyphenol pretreatment. A possible polyphenol‐sensitized ALD mechanism is proposed involving initial island nucleation followed by film intergrowth. This polyphenol sensitization strategy enriches the functionalization toolbox in material science, interface engineering, and environmental science.     

Sacrificial‐Layer Atomic Layer Deposition for Fabrication of Non‐Close‐Packed Inverse‐Opal Photonic Crystals

A method is presented for predicting and precisely controlling the structure of photonic crystals fabricated using sacrificial‐layer atomic layer deposition. This technique provides a reliable method for fabrication of high‐quality non‐close‐packed inverse shell opals with large static tunability and precise structural control. By using a sacrificial layer during opal infiltration, the inverse‐opal pore size can be increased with sub‐nanometer resolution and without distorting the lattice to allow for a high degree of dielectric backfilling and increased optical tunability. For a 10 % sacrificial layer, static tunability of 80 % is predicted for the inverse opal. To illustrate this technique, SiO₂ opal templates were infiltrated using atomic layer deposition of ZnS, Al₂O₃, and TiO₂. Experimentally, a static tunability of over 600 nm, or 58 %, was achieved and is well described by both a geometrical model and a numerical‐simulation algorithm. When extended to materials of higher refractive index, this method will allow the facile fabrication of 3D photonic crystals with optimized photonic bandgaps.     

Low‐Temperature Growth of SiO2 Films by Plasma‐Enhanced Atomic Layer Deposition

Silicon dioxide (SiO₂) films prepared by plasma‐enhanced atomic‐layer deposition were successfully grown at temperatures of 100 to 250 °C, showing self‐limiting characteristics. The growth rate decreases with an increasing deposition temperature. The relative dielectric constants of SiO₂ films are ranged from 4.5 to 7.7 with the decrease of growth temperature. A SiO₂ film grown at 250 °C exhibits a much lower leakage current than that grown at 100°C due to its high film density and the fact that it contains deeper electron traps.     

原子层淀积技术应用于太阳电池的研究进展

原子层淀积(ALD)是一种先进的纳米级薄膜生长技术,在微电子和光电子领域有着广泛的应用前景,尤其在提高太阳电池的光电转换效率方面正发挥越来越大的作用,很可能成为下一代太阳电池工艺中的重要方法。文章综述了近年来ALD技术在太阳电池领域的应用研究进展,详细介绍了ALD技术应用在不同类型太阳电池的最新研究成果和存在的问题,并对其发展趋势进行了展望。     

Conformal Hermetic Sealing of Wireless Microelectronic Implantable Chiplets by Multilayered Atomic Layer Deposition (ALD)

A hermetic sealing method of sub‐millimeter‐sized microelectronic chiplets for wireless body implants is presented by ultrathin and electromagnetically transparent atomic layer deposition (ALD) coatings. Fully 3D conformal encapsulation of wirelessly powered microdevices is demonstrated both with and without opening windows for electrophysiological measurements. The chiplets embedding custom application‐specific integrated circuits (ASICs) with radio frequency (RF) transmitters are encapsulated by a stack of alternating layers of hafnium oxide and silicon dioxide to maximize impermeability of water and ionic penetration while minimizing the volume of the packaging material. The hermeticity of the devices is characterized through accelerated aging tests in saline at T = 87 °C, while continued functionality is monitored via evaluation of backscattered RF signals (near 1 GHz) to ascertain possible degradation and electronic failure. Earliest failures of wirelessly functional devices occur after more than 180 d of immersion at 87 °C. Wireless devices having opening windows through the ALD envelope show no signs of degradation for >100 d. This implies an equivalent lifetime >10 years at T = 37 °C. This approach is readily scalable to high throughput batch processing of hundreds of microchiplets, offering a methodology for hermetic packaging of microscale biomedical chronic implants.     

Electrode Engineering by Atomic Layer Deposition for Sodium‐Ion Batteries: From Traditional to Advanced Batteries

Sodium‐ion batteries (SIBs) have emerged as one of the most promising and competitive energy storage systems due to abundant sodium resources and its environmentally friendly features. However, further improvements in the engineering of the SIB electrode/electrolyte interphase—which directly determines the Na‐ion transfer behavior, material structure stability, and sodiation/desodiation property—are highly recommended to meet the continuously increasing requirements for secondary power sources. Reasonably speaking, to promote SIBs, the advanced and controllable interphase/electrode engineering approach exhibits promise by rationally designing the bulk electrode and generating a well‐defined interphase. Atomic layer deposition (ALD) technology, with atomic‐scale deposition, superior uniformity, excellent conformality, and a self‐limiting nature, is thus expected to address the current challenges facing SIBs in terms of low energy density, limited cycling life, and structural instability, and to promote innovations such as multifunctional electrodes and nanostructured materials for advanced SIBs. This review summarizes and discusses the most recent advancements in the interphase engineering of SIBs by ALD via modifying traditional electrodes and designing advanced electrodes (such as 3D, organic, and protected sodium metal electrodes). Furthermore, based on the recent critical progress and current scientific understanding, future perspectives for the engineering of next‐generation SIB electrodes by ALD can be provided.     

原子层沉积法制备高反射率的分布式布拉格反射镜

为提高GaN基发光二极管(LED)的发光强度,制备TiO₂/Al₂O₃分布式布拉格反射器(DBR)来提高其外量子效率是一种有效的方法。原子层沉积(ALD)法所制备的薄膜具有良好的均匀性,适合用来制备反射器材料。同时,TiN薄膜具有良好的类金属性质,且与TiO₂之间具有良好的粘附性,因此在DBR基础上再采用TiN反射层可以将反射率进一步提高。Matlab软件模拟结果表明,3~6周期厚的DBR,其反射率随厚度增加而提高。其中6周期DBR的反射率为95%,加上TiN薄膜后反射率可以得到进一步提高。实验结果与模拟结果吻合,6周期DBR+TiN结构的反射率达到99%。给带有该结构的LED注入50mA电流时,LED光输出功率(LOP)相对没有该结构的器件提升了约68.3%。     

GaAs衬底上等离子体增强原子层沉积GaN薄膜

采用等离子体增强原子层沉积(PEALD)技术在斜切的砷化镓(GaAs)衬底上低温沉积了氮化镓(GaN)薄膜,对生长过程、表面机制以及界面特性等进行分析,得到GaN在215～270℃的温度窗口内生长速度(Growth-Per-Cycle, GPC)为0.082 nm/cycle,并从表面反应动力学和热力学方面对GPC的变化进行了分析。研究发现,生长的GaN薄膜为多晶,具有六方纤锌矿结构,且出现(103)结晶取向。在GaN/GaAs界面处观察到约1 nm厚的非晶层,这可能与生长前衬底表面活性位点的限制和前驱体的空间位阻效应有关。值得注意的是,在沉积的GaN薄膜中,所有的N皆与Ga以Ga-N键结合生成GaN,但是存在少部分Ga形成了Ga-O键和Ga-Ga键。这种成键方式,可能与GaN薄膜中存在的缺陷和杂质有关。     

Atomic Layer Deposited Non‐Noble Metal Oxide Catalyst for Sodium–Air Batteries: Tuning the Morphologies and Compositions of Discharge Product

Catalysts can play a critical role in the development of sodium–air batteries (SABs). Atomic layer deposition (ALD) technology enables rational design and atomic utilization of catalyst by homogenously distributing catalytically active material on a variety of substrates. Here, a novel hierarchical nanostructured Co₃O₄ is decorated on carbon nanotubes by ALD (CNT@Co₃O₄) and used as a catalyst for SABs. CNT@Co₃O₄ demonstrates better performance and longer cycle life than a mechanically mixed CNT/Co₃O₄ nanocomposite. Well‐dispersed ALD Co₃O₄ catalyst on CNTs, which serves as functionalized active sites, enables rapid electron exchange and high oxygen reduction/evolution activities. Synchrotron‐based X‐ray analysis including X‐ray absorption near edge structure, extended X‐ray absorption fine structure, and scanning transmission X‐ray microscopy characterization techniques have been employed to elucidate the activity of Co₃O₄ and to investigate the nanoscale discharge product distribution found in SABs. This analysis reveals that Co₃O₄ catalyst can promote the electrochemical decomposition of sodium peroxide, superoxide, and carbonates. The role of the catalyst in SABs is clarified and discussed in detail.     

Aluminum Oxide at the Monolayer Limit via Oxidant-Free Plasma-Assisted Atomic Layer Deposition on GaN

Atomic layer deposition (ALD) is an essential tool in semiconductor device fabrication that allows the growth of ultrathin and conformal films to precisely form heterostructures and tune interface properties. The self-limiting nature of the chemical reactions during ALD provides excellent control over the layer thickness. However, in contrast to idealized growth models, it is challenging to create continuous monolayers by ALD because surface inhomogeneities and precursor steric interactions result in island growth. Thus, the ability to create closed monolayers by ALD would offer new opportunities for controlling interfacial charge and mass transport in semiconductor devices, as well as for tailoring surface chemistry. Here, encapsulation of c-plane gallium nitride (GaN) with ultimately thin (≈3 Å) aluminum oxide (AlO_x) is reported, which is enabled by the partial conversion of the GaN surface oxide into AlO_x using sequential exposure to trimethylaluminum (TMA) and hydrogen plasma. Introduction of monolayer AlO_x decreases the work function and enhances reactivity with phosphonic acids under standard conditions, which results in self-assembled monolayers with densities approaching the theoretical limit. Given the high reactivity of TMA with surface oxides, the presented approach likely can be extended to other dielectrics and III–V-based semiconductors, with relevance for applications in optoelectronics, chemical sensing, and (photo)electrocatalysis.     

Low Temperature Stabilization of Nanoscale Epitaxial Spinel Ferrite Thin Films by Atomic Layer Deposition

In this work heteroepitaxial stabilization with nanoscale control of the magnetic Co₂FeO₄ phase at 250 °C is reported. Ultrasmooth and pure Co₂FeO₄ thin films (5–25 nm) with no phase segregation are obtained on perovskite SrTiO₃ single crystal (100) and (110) oriented substrates by atomic layer deposition (ALD). High resolution structural and chemical analyses confirm the formation of the Co‐rich spinel metastable phase. The magneto‐crystalline anisotropy of the Co₂FeO₄ phase is not modified by stress anisotropy because the films are fully relaxed. Additionally, high coervice fields, 15 kOe, and high saturation of magnetization, 3.3 μ_B per formula unit (at 10 K), are preserved down to 10 nm. Therefore, the properties of the ALD‐Co₂FeO₄ films offer many possibilities for future applications in sensors, actuators, microelectronics, and spintronics. In addition, these results are promising for the use of ALD compared to the existing thin‐film deposition techniques to stabilize epitaxial multicomponent materials with nanoscale control on a wide variety of substrates for which the processing temperature is a major drawback.     

Indium Tin Oxide Thin Films Grown on Polyethersulphone (PES) Substrates by Pulsed‐Laser Deposition for Use in Organic Light‐Emitting Diodes

High quality indium tin oxide (ITO) thin films were grown by pulse laser deposition (PLD) on flexible polyethersulphone (PES) substrates. The electrical, optical, and surface morphological properties of these films were examined as a function of substrate temperature and oxygen pressure. ITO thin films, deposited by PLD on a PES substrate at room temperature and an oxygen pressure of 15 mTorr, have a low electrical resistivity of 2.9×10^?4 Ω cm and a high optical transmittance of 84 % in the visible range. They were used as the anode in organic light‐emitting diodes (OLEDs). The maximum electro luminescence (EL) and current density at 100 cd/m² were 2500 cd/m² and 2 mA/cm², respectively, and the external quantum efficiency of the OLEDs was found to be 2.0 %.