Characteristics and properties of metal aluminum thin films prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited Al films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.     

Influences of annealing on structural and compositional properties of Al_2O_3 thin films grown on 4H–SiC by atomic layer deposition

Annealing effects on structural and compositional performances of Al_2O_3 thin films on 4H–Si C substrates are studied comprehensively. The Al_2O_3 films are grown by atomic layer deposition through using trimethylaluminum and H_2 O as precursors at 300?C, and annealed at various temperatures in ambient N_2 for 1 min. The Al_2O_3 film transits from amorphous phase to crystalline phase as annealing temperature increases from 750?C to 768?C. The refractive index increases with annealing temperature rising, which indicates that densification occurs during annealing. The densification and grain formation of the film upon annealing are due to crystallization which is relative with second-nearest-neighbor coordination variation according to the x-ray photoelectron spectroscopy(XPS). Although the binding energies of Al 2p and O 1s increase together during crystallization, separations between Al 2p and O 1s are identical between as-deposited and annealed sample, which suggests that the nearest-neighbour coordination is similar.     

等离子增强原子层沉积低温生长GaN薄膜

采用等离子增强原子层沉积技术在低温下于单晶硅衬底上成功生长了Ga N多晶薄膜,利用椭圆偏振仪、低角度掠入射X射线衍射仪、X射线光电子能谱仪对薄膜样品的生长速率、晶体结构及薄膜成分进行了表征和分析.结果表明,等离子增强原子层沉积技术生长Ga N的温度窗口为210—270?C,薄膜在较高生长温度下呈多晶态,在较低温度下呈非晶态;薄膜中N元素与大部分Ga元素结合成N—Ga键生成Ga N,有少量的Ga元素以Ga—O键存在,多晶Ga N薄膜含有少量非晶态Ga_2O_3.     

Plasmonic tuning of aluminum doped zinc oxide nanostructures by atomic layer deposition

Currently there is a strong interest in plasmonic materials operating in the near‐infrared (NIR), however, conventional metals such as gold and silver possess high optical losses in this region. In this work we demonstrate localized surface plasmon resonances (LSPRs) with low loss in the NIR region by utilizing atomic layer deposition to deposit thin films of aluminium doped zinc oxide onto silicon nanopillars created via nanopshere lithography. The deposited films have excellent conformality and the LSPRs can be tuned from the mid‐infrared to the NIR by controlling the doping concentration, deposition temperature and nanostructure morphology. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Preparation of tantalum oxide thin films by photo-assisted atomic layer deposition

Tantalum oxide thin films were prepared by photo-assisted atomic layer deposition (Photo-ALD) in the substrate temperature range of 170–400 °C using Ta(OC₂H₅)₅ and H₂O as precursors. The constant growth rates of 0.42 and 0.47 Å per cycle were achieved for the films grown by normal ALD and Photo-ALD, respectively. The increased growth rate in Photo-ALD is probably due to the reactive surface by photon energy and faster surface reaction. In Photo-ALD, however, the constant growth rate started at lower temperature of 30 °C and one cycle time shortened up to 5.7 s than that of normal ALD. The films grown by normal ALD and Photo-ALD were amorphous and very smooth (0.21–0.35 nm) as examined by X-ray diffractometer and atomic force microscopy, respectively. Also, the refractive index was found to be 2.12–2.16 at the substrate temperature of 190–300 °C, similar to that of the film grown by normal ALD. However, the remarkably low leakage current density of 0.6×10⁻⁶ A/cm² to 1×10⁻⁶ A/cm² at applied field of 1 MV/cm is several order of magnitude smaller than that of normal ALD, probably due to the presence of reactive atom species.     

等离子增强原子层沉积低温生长AlN薄膜

采用等离子增强原子层沉积技术在单晶硅基体上成功制备了AlN晶态薄膜, 利用椭圆偏振仪、原子力显微镜、小角掠射X射线衍射仪、高分辨透射电子显微镜、 X射线光电子能谱仪对样品的生长速率、表面形貌、晶体结构、薄膜成分进行了表征和分析, 结果表明, 采用等离子增强原子层沉积制备AlN晶态薄膜的最低温度为200 ℃, 薄膜表面平整光滑, 具有六方纤锌矿结构与(100)择优取向, Al_2p与N_1S的特征峰分别为74.1 eV与397.0 eV, 薄膜中Al元素与N元素以Al-N键相结合, 且成分均匀性良好. 关键词： 氮化铝 等离子增强原子层沉积 低温生长 晶态薄膜     

Patterned deposition by plasma enhanced spatial atomic layer deposition

An atmospheric pressure plasma enhanced atomic layer deposition reactor has been developed, to deposit Al₂O₃ films from trimethyl aluminum and an He/O₂ plasma. This technique can be used for 2D patterned deposition in a single in‐line process by making use of switched localized plasma sources. It was observed that the sharpness of the patterns is primarily influenced by the concentration of reactive plasma species and by the dimensions of the plasma source. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

原子层沉积法 生长ZnO的性质与前驱体源量的关系研究

介绍了新型材料ZnO的各项性能,并采用原子层沉积方法制备新型材料ZnO. 实验中采用二乙基锌(DEZn) 和水作为生长ZnO的前驱体源, 在蓝宝石衬底上生长ZnO; 采用氮气作为载气, 生长温度为180℃. 通过改变在实验中的通入锌源的时间, 探索不同的DEZn的源的量对薄膜的成分(Zn/O)、薄膜的厚度、生长速率、晶型、 表面形貌、三维形貌以及粗糙度的影响. 关键词： 氧化锌 原子层沉积 Zn/O     

Low-temperature plasma enhanced atomic layer deposition of large area HfS_2 nanocrystal thin films

Hafnium disulfide(HfS2) is a promising two-dimensional material for scaling electronic devices due to its higher carrier mobility, in which the combination of two-dimensional materials with traditional semiconductors in the framework of CMOS-compatible technology is necessary. We reported on the deposition of HfS2 nanocrystals by remote plasma enhanced atomic layer deposition at low temperature using Hf(N(CH3)(C2H5))4 and H2S as the reaction precursors. Selflimiting reaction behavior was observed at the deposition temperatures ranging from 150℃ to 350℃, and the film thickness increased linearly with the growth cycles. The uniform HfS2 nanocrystal thin films were obtained with the size of nanocrystal grain up to 27 nm. It was demonstrated that higher deposition temperature could enlarge the grain size and improve the HfS2 crystallinity, while causing crystallization of the mixed HfO2 above 450℃. These results suggested that atomic layer deposition is a low-temperature route to synthesize high quality HfS2 nanocrystals for electronic device or electrochemical applications.     

Influence of annealing temperature on passivation performance of thermal atomic layer deposition Al_2O_3 films

Chemical and field-effect passivation of atomic layer deposition （ALD） Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy （TEM） and X-ray photoelectron spectroscopy （XPS）, respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.     

气相沉积技术在原子制造领域的发展与应用

随着未来信息器件朝着更小尺寸、更低功耗和更高性能方向的发展,构建器件的材料尺寸将进一步缩小.传统的"自上而下"技术在信息器件发展到纳米量级时遇到瓶颈,而气相沉积技术由于其能在原子尺度构筑纳米结构引起极大关注,被认为是最有潜力突破现有制造极限进而在原子尺度构造、搭建物质形态的"自下而上"方法.本文重点讨论适用于低维材料的...     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.     

Effects of AlN nucleation layer thickness on crystal quality of AlN grown by plasma-assisted molecular beam epitaxy

In this paper,the effects of thickness of AlN nucleation layer grown at high temperature on AlN epi-layer crystalline quality are investigated.Crack-free AlN samples with various nucleation thicknesses are grown on sapphire substrates by plasma-assisted molecular beam epitaxy.The AlN crystalline quality is analysed by transmission electron microscope and x-ray diffraction (XRD) rocking curves in both (002) and (102) planes.The surface profiles of nucleation layer with different thicknesses after in-situ annealing are also analysed by atomic force microscope.A critical nucleation thickness for realising high quality AlN films is found.When the nucleation thickness is above a certain value,the (102) XRD full width at half maximum (FWHM) of AlN bulk increases with nucleation thickness increasing,whereas the (002) XRD FWHM shows an opposite trend.These phenomena can be attributed to the characteristics of nucleation islands and the evolution of crystal grains during AlN main layer growth.     

原子层沉积HfO2薄膜的激光损伤特性分析

以目前激光惯性约束聚变中应用最广泛的高折射率材料二氧化铪(HfO2)为研究对象,在熔石英基底上分别采用TEMAH和HfCl4前驱体制备了HfO2薄膜,沉积温度分别为100,200和300 ℃。采用椭偏仪和激光量热计对薄膜的光学性能进行了测量分析,采用X射线衍射仪(XRD)对薄膜的微结构进行了测量。最后在小口径激光阈值测量平台上按照1-on-1测量模式对薄膜的损伤阈值进行了测试,并采用扫描电子显微镜（SEM）对损伤形貌进行了分析。研究表明,用同一种前驱体源时,随着沉积温度升高,薄膜折射率增加,吸收增多,损伤阈值降低。在相同温度下,采用有机源制备的薄膜更容易在薄膜内部形成有机残留,导致薄膜吸收增加,损伤阈值降低。采用HfCl4作为前驱体源在100℃制备氧化铪薄膜时,损伤阈值能够达到31.8 J/cm2 (1064 nm,3 ns)。     

Double‐layer channel structure based ZnO thin‐film transistor grown by atomic layer deposition

A double channel structure has been used by depositing a thin amorphous‐AlZnO (a‐AZO) layer grown by atomic layer deposition between a ZnO channel and a gate dielectric to enhance the electrical stability. The effect of the a‐AZO layer on the electrical stability of a‐AZO/ZnO thin‐film transistors (TFTs) has been investigated under positive gate bias and temperature stress test. The use of the a‐AZO layer with 5 nm thickness resulted in enhanced subthreshold swing and decreased V_th shift under positive gate bias/temperature stress. In addition, the falling rate of the oxide TFT using a‐AZO/ ZnO double channel had a larger value (0.35 eV/V) than that of pure ZnO TFT (0.24 eV/V). These results suggest that the interface trap density between dielectric and channel was reduced by inserting a‐AZO layer at the interface between the channel and the gate insulator, compared with pure ZnO channel. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于多孔氧化铝和单原子沉积技术的颜色调控方法研究

本文通过建立多孔氧化铝(porous alumina,PA)的物理模型及理论分析,提出与发展了一种基于PA和单原子沉积(atomic layer deposition,ALD)技术的颜色调控新方法.以实验制备的PA样品为原型,对孔径相同、孔中心距相同但孔深不同的一系列PA模板进行了颜色调控的仿真,揭示了调控色随孔深变化的规律;通过控制在草酸溶液中的阳极氧化时间,实验制备出平均孔径40 nm、平均孔中心距100 nm、孔深分别为296 nm和373 nm的两个PA样品;之后采用ALD技术在它们表面均沉积一层 关键词： 多孔氧化铝 颜色调控 单原子沉积     

Controlled growth of rutile TiO2 by atomic layer deposition on oxidized ruthenium

Crystalline rutile TiO₂ films were grown by atomic layer deposition on oxidized Ru electrodes using a titanium methoxide as the metal precursor and O₃ as the oxidant. A protective layer of ～0.3 nm TiO₂ grown with H₂O as the oxidant was first deposited in order to avoid etching of the Ru bottom electrode by the O₃ used for the growth of the TiO₂ (bulk) layer. Electrical evaluation of the capacitor stacks with TiO₂ as dielectric, RuO₂/Ru and Pt as the bottom and top electrodes respectively, resulted in superior characteristics of the rutile phase as compared to the anatase. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Impact of substrate temperature and film thickness on the interfacial evolution during atomic layer deposition of HfO2 on InP

The effects of both the deposition temperature and the HfO₂ film thickness on the interfacial layer (IL) evolution were studied when tetrakis(ethylmethylamino)hafnium and H₂O based atomic layer deposition (ALD) was performed on InP substrates. While the self‐cleaning effect resulted in an IL‐free structure after formation of ～2 nm thick HfO₂ at 200 °C and 250 °C, substantial IL growth occurred at 300 °C, probably due to simultaneous InP oxidation. Following further growth to ～8 nm at 300 °C, the IL was almost removed and, in particular, a significant In incorporation into the HfO₂ film was observed, which was attributed to IL decomposition and subsequent out‐diffusion of the constituent elements. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

原子层沉积方法制备核-壳型纳米材料研究

采用原子层沉积方法在碳黑纳米颗粒表面分别沉积Al₂O₃, ZnO, TiO₂和Pt, 成功制备出核-壳型纳米材料. 通过高分辨率透射电子显微镜、X射线光电子能谱仪、 能谱仪对材料的表面形貌、晶体结构、薄膜成分进行了表征和分析. 结果表明, 原子层沉积方法是制备核壳型纳米材料的理想方法. 此外, 还分析了采用原子层沉积方法沉积不同材料, 所生长的薄膜材料有单晶、多晶、非晶等多种存在形式的形成原因. 关键词： 原子层沉积 核-壳型纳米材料 碳黑纳米颗粒