Thickness dependent barrier performance of permeation barriers made from atomic layer deposited alumina for organic devices

Organic devices like organic light emitting diodes (OLEDs) or organic solar cells degrade fast when exposed to ambient air. Hence, thin-films acting as permeation barriers are needed for their protection. Atomic layer deposition (ALD) is known to be one of the best technologies to reach barriers with a low defect density at gentle process conditions. As well, ALD is reported to be one of the thinnest barrier layers, with a critical thickness – defining a continuous barrier film – as low as 5–10 nm for ALD processed Al₂O₃. In this work, we investigate the barrier performance of Al₂O₃ films processed by ALD at 80 °C with trimethylaluminum and ozone as precursors. The coverage of defects in such films is investigated on a 5 nm thick Al₂O₃ film, i.e. below the critical thickness, on calcium using atomic force microscopy (AFM). We find for this sub-critical thickness regime that all spots giving raise to water ingress on the 20 × 20 μm² scan range are positioned on nearly flat surface sites without the presence of particles or large substrate features. Hence below the critical thickness, ALD leaves open or at least weakly covered spots even on feature-free surface sites. The thickness dependent performance of these barrier films is investigated for thicknesses ranging from 15 to 100 nm, i.e. above the assumed critical film thickness of this system. To measure the barrier performance, electrical calcium corrosion tests are used in order to measure the water vapor transmission rate (WVTR), electrodeposition is used in order to decorate and count defects, and dark spot growth on OLEDs is used in order to confirm the results for real devices. For 15–25 nm barrier thickness, we observe an exponential decrease in defect density with barrier thickness which explains the likewise observed exponential decrease in WVTR and OLED degradation rate. Above 25 nm, a further increase in barrier thickness leads to a further exponential decrease in defect density, but an only sub-exponential decrease in WVTR and OLED degradation rate. In conclusion, the performance of the thin Al₂O₃ permeation barrier is dominated by its defect density. This defect density is reduced exponentially with increasing barrier thickness for alumina thicknesses of up to at least 25 nm.     

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.     

原子层沉积低温生长α-MoO3薄膜

以六羰基钼和氧气为前驱体,通过等离子增强原子层沉积技术（PE-ALD）在硅基片上实现了α-MoO₃薄膜的低温制备。利用X射线衍射仪、扫描电子显微镜、原子力显微镜、X射线光电子能谱仪等手段对薄膜的晶体结构、表面形貌及薄膜成分进行表征和分析。研究发现衬底温度和氧源脉冲时间对MoO₃薄膜的晶体结构和表面形貌变化起关键作用。当衬底温度为170℃及以上时所制备的薄膜为α-MoO₃;适当延长ALD单循环中的氧源脉冲时间有利于低温沉积沿（0k0）高度择优取向的MoO₃薄膜。根据对不同厚度MoO₃薄膜表面的原子力显微图片分析,MoO₃薄膜为岛状生长模式。     

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.     

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH₃ plasma as the phosphorus source and an extra H₂ plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.     

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.     

Pt coated Cr2O3 thin films for resistive gas sensors

The resistive response of atomic layer deposited thin epitaxial α-Cr₂O₃(0 0 1) films, to H₂ and CO in air, was studied. The films were covered with Pt nanoislands formed by electron-beam evaporation of a sub-monolayer amount of the material. The gas measurements were performed at 250°C and 450°C. These temperatures led to different proportion of chemical states, Pt²⁺ and Pt⁴⁺, to which the Pt oxidized. The modification was ascertained by the X-ray photoelectron spectroscopy method. As a result of the modification, the response was fast at 250°C, but slowed at 450°C. A disadvantageous abundance of Pt⁴⁺ arising at 450°C in air could be diminished by high-vacuum annealing thus restoring the response properties of the system at 250°C.      

On the relative stability of cobalt‐ and nickel‐based amidinate complexes against β‐migration

We present a first‐principles study on the relative stability of cobalt‐ and nickel‐based amidinate complexes against β‐migration using density functional theory. Factors that influence the reactivity of these compounds were carefully addressed and the calculated molecular structures are in excellent agreement with the available crystal structural data. Reaction energies as well as activation barriers of β‐migration were evaluated. The predicted relative stability of the selected compounds is consistent with experimental observations. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009