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.     

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     

Interactions between tri-methylaluminum molecules and their effect on the reaction of tri-methylaluminum with an OH-terminated Si (0 0 1) surface

We studied the interaction between tri-methylaluminum (Al(CH₃)₃, TMA) molecules and their effect on TMA reactions with a fully OH-terminated Si (0 0 1) surface for initial aluminum oxide thin-film growth using density functional theory. The reaction between an adsorbed TMA and the surface produced a di-methylaluminum (-Al(CH₃)₂, DMA) group, and further reaction to a uni-methylaluminum (-AlCH₃, UMA) group with energy barriers of 0.50 and 0.21 eV, respectively. A second TMA adsorbed near the already adsorbed TMA, DMA, or UMA group showed higher energy barriers (0.68-1.01 eV) for its reaction to produce a DMA group due to the interaction between them. Therefore, the fully OH-terminated Si (0 0 1) surface would be covered by the mixture of the adsorbed TMA and UMA groups at an intermediate surface temperature.     

Sub-100 nm ALD-assisted nanoimprint lithography for realizing vertical organic transistors with high ON/OFF ratio and high output current

We introduced a conformal atomic-layer-deposited aluminum oxide layer to cover the imprint mold to reduce the feature size and to strengthen the mold durability. A nano-hole array pattern with diameter down to 85 nm was successfully transferred to sample substrate to fabricate a vertical organic transistor. The Imprint vertical organic transistor exhibited high output current density as 4.35 cm²/V s and high ON/OFF current ratio as 11,000 at a low operation voltage as 1.5 V.     

Effect of wet chemical substrate pretreatment on the growth behavior of Ta(N) films deposited by thermal ALD

The deposition of ultra thin Ta(N) films by ALD is a possibility to achieve conformal film thickness and suitable step coverage for microelectronic applications. Due to the sorption of a precursor molecule to the substrate surface, the chemical interface conditions are important. In the present study selected substrate pretreatments were investigated by in situ XPS and spectroscopic ellipsometry in reference to the amount of carbon containing contamination and oxygen and in reference to the ALD growth rate of Ta(N) films. Furthermore, surface roughness was measured by AFM and will be discussed in dependence on the individual pretreatment and the ALD Ta(N) cycle number.