Nanocoating individual cohesive boron nitride particles in a fluidized bed by ALD

Experiments are conducted with alumina (Al₂O₃) deposition on a wide size range of hexagonal boron nitride (BN) platelet-like particles. Successful deposition of alumina films on these particles, with film thickness controllable at the Angstrom level, is observed based upon TEM imaging, ICP-AES, particle size distributions, and surface area analysis. While fluidizing, fine BN particles aggregate in the bed. The aggregates are the entities fluidizing, not the primary particles. However, individual particles are coated using Atomic Layer Deposition (ALD), not aggregates. Since ALD is a surface chemistry phenomenon, the films grow uniformly on every primary particle. BN particles are small platelets with different functional groups on the basal planes and edge planes. A small exposure to reagents [2.5×10⁶ Langmuir (L) per reagent per cycle], will only coat the edge planes of uncoated BN particles. A larger dose of 1×10⁸ L will coat the entire uncoated BN particle (edge and basal planes). After 10 ALD cycles of the 1×10⁸ L dose, the exposures can be reduced to 1×10⁶ L as the film is then growing on alumina and not BN. Peel strength data indicate that adhesion between the coated particles and a cured epoxy in a filled composite is ∼25% stronger than that of uncoated particles and the epoxy. The overall thermal conductivity drops ∼17% for an identical filler loading as expected due to the additional thermal resistance added by the film. However, the viscosity of an epoxy resin loaded with coated BN is as much as five times lower than that of the resin loaded with the same amount of uncoated BN. These results indicate that the loading of Al₂O₃ nanocoated BN particles in an epoxy matrix can be substantially increased relative to that of uncoated particles. The thermal conductivity of the more highly filled composite will be increased without adversely impacting filled resin viscosity or the peel strength of the cured material. This is the first reported study indicating that cohesive primary particles that fluidize as aggregates in a fluidized bed can be individually coated with a nano-thick ceramic film using ALD.     

Freestanding hierarchical porous carbon film derived from hybrid nanocellulose for high-power supercapacitors

Nanocellulose is a sustainable and eco-friendly nanomaterial derived from renewable biomass.In this study,we utilized the structural advantages of two types of nanocellulose and fabricated freestanding carbonized hybrid nanocellulose films as electrode materials for supercapacitors.The long cellulose nanofibrils (CNFs) formed a macroporous framework,and the short cellulose nanocrystals were assembled around the CNF framework and generated micro/mesopores.This two-level hierarchical porous structure was successfully preserved during carbonization because of a thin atomic layer deposited (ALD) Al2O3 conformal coating,which effectively prevented the aggregation of nanocellulose.These carbonized,partially graphitized nanocellulose fibers were interconnected,forming an integrated and highly conductive network with a large specific surface area of 1,244 m2·g-1.The two-level hierarchical porous structure facilitated fast ion transport in the film.When tested as an electrode material with a high mass loading of 4 mg·cm-2 for supercapacitors,the hierarchical porous carbon film derived from hybrid nanocellulose exhibited a specific capacitance of 170 F.g-1and extraordinary performance at high current densities.Even at a very high current of 50 A·g-1,it retained 65％ of its original specific capacitance,which makes it a promising electrode material for high-power applications.     

在线KPLS建模方法及在磨机负荷参数集成建模中的应用

针对过程非线性、基于历史数据构建的离线模型泛化性差以及基于滑动窗口 和每样本递推更新的在线建模方法难以均衡建模精度和建模速度等问题, 提出了一种在线 核偏最小二乘(On-line kernel partial least squares, OLKPLS)建模方法. 该方法依据新样本与建模样本间的近似线性依靠(Approximate linear dependence, ALD)值和代表工业过程特性漂移幅度的 阈值, 选择有价值样本更新KPLS模型, 并采用合成数据和Benchmark平台数据对该方法进 行了仿真验证. 针对基于离线历史数据建立的融合多传感器信息的磨机负荷参数集成模型难以适应磨 矿过程时变特性的问题, 提出了基于OLKPLS和在线自适应加权融合算法的在线集成建模方 法, 并通过实验球磨机的实际运行数据仿真验证了方法的有效性.     

氧化铝增强的PdSe2/Si异质结光电探测器

为了降低暗电流,通过原子层沉积(ALD)生长了一层氧化铝(Al₂O₃)隧穿层,制备了PdSe₂/Al₂O₃/Si异质结光电探测器.通过优化Al₂O₃层的厚度,使得该探测器实现了高速和宽光谱响应.研究结果表明,在波长为808 nm的光照射和-2 V偏压下,所制备的光电探测器与未生长Al₂O₃的器件相比,暗电流降低了约3个数量级,器件的光响应度达到了约为0.31 A/W,对应的比探测率约为2.5×10¹² Jones,器件在零偏压下表现出明显的自驱动效应.经过循环测试1 200次后,器件保持良好的光响应.器件响应的上升时间和下降时间分别为7.1和15.6μs.结果表明,在二维层状半导体材料与Si之间引入Al₂O₃隧穿层,可以有效地降低器件的暗电流,有利于高性能的Si基光电探测器的制备.     

Thin‐film encapsulated white organic light top‐emitting diodes using a WO3/Ag/WO3 cathode to enhance light out‐coupling

An alternative design of a semitransparent cathode for top‐emission white‐fluorescent organic light‐emitting diodes (OLEDs) has been investigated. The scope of this study was to improve the luminance of OLEDs used for displays while keeping the current density versus voltage characteristic unchanged for addressing purposes. The use of an optical simulation tool allowed the optimization of the tri‐layer cathode WO₃/Ag/WO₃ to increase the light out‐coupling coefficient of the device leading to an increased white emission compared with a reference device with a Ca/Ag cathode. An increase of ~40% in luminance has been calculated by simulation and experimentally confirmed. The p‐i‐n OLED structure underneath the tri‐layer cathode allowed an efficient injection of electrons independently from the work function of WO₃. The WO₃/Ag/WO₃ cathode has been also confirmed to be compatible with the atomic layer deposition technique for thin film encapsulation. Finally, lifetime measurements up to 600 h have been carried out to quantify the enhancements induced by the new cathode compared with the control device. It has been found that lifetimes of both cathode architectures are similar on this time scale, while the WO₃/Ag/WO₃ cathode shows a lower voltage drift versus aging.     

纳米二氧化钒薄膜的制备及其特性研究

采用原子层沉积(ALD)方法,分别以VO(OC3H7)3和H2 O2为钒源和氧源,在载玻片基底上沉积钒氧化物薄膜;在还原气氛的管式炉中,对钒氧化物薄膜进行还原退火结晶,进而得到VO2薄膜晶体.通过扫描电镜(SEM)、X-射线衍射(XRD)及X-射线光电子能谱(XPS)研究所制备的钒氧化物薄膜表面形貌、晶体结构以及组分的变化;利用傅里叶红外光谱(FT-IR)对VO2薄膜的红外透射性进行测试分析.结果表明:ALD所制备的薄膜以非晶态V2O5、VO2和V2O3为主;在通以还原气氛(95％Ar,5％H2)并500℃热处理2h后得到以(011)择优取向的单斜金红石纳米VO2薄膜,VO2晶体薄膜相变前后红外透过率突变量较大.     

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.     

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.     

Atomic-layer-deposited Al2O3 and HfO2 on GaN: A comparative study on interfaces and electrical characteristics

Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ films were deposited on n-type GaN using atomic layer deposition (ALD). The interfacial layer of GaON and HfON was observed between HfO₂ and GaN, whereas the absence of an interfacial layer at Al₂O₃/GaN was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The dielectric constants of Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ calculated from the C-V measurement are 9, 16.5, and 13.8, respectively. The Al₂O₃ employed as a template in the composite structure has suppressed the interfacial layer formation during the subsequent ALD-HfO₂ and effectively reduced the gate leakage current. While the dielectric constant of the composite HfO₂/Al₂O₃ film is lower than that of HfO₂, the composite structure provides sharp oxide/GaN interface without interfacial layer, leading to better electrical properties.     

Atomic layer chemical vapour deposition of copper

Copper films with (1 1 1) texture are of crucial importance in integrated circuit interconnects. We have deposited strongly (1 1 1)-textured thin films of copper by atomic layer deposition (ALD) using [2,2,6,6-tetramethyl-3,5-heptadionato] Cu(II), Cu(thd)₂, as the precursor. The dependence of the microstructure of the films on ALD conditions, such as the number of ALD cycles and the deposition temperature was studied by X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy. Analysis of (1 1 1)-textured films shows the presence of twin planes in the copper grains throughout the films. SEM shows a labyrinthine structure of highly connected, large grains developing as film thickness increases. This leads to low resistivity and suggests high resistance to electromigration.