Versatile sputtering technology for Al2O3 gate insulators on graphene

Abstract

We report a novel, sputtering-based fabrication method of Al₂O₃ gate insulators on graphene. Electrical performance of dual-gated mono- and bilayer exfoliated graphene devices is presented. Sputtered Al₂O₃ layers possess comparable quality to oxides obtained by atomic layer deposition with respect to a high relative dielectric constant of about 8, as well as low-hysteresis performance and high breakdown voltage. We observe a moderate carrier mobility of about 1000 cm² V^?1 s^?1 in monolayer graphene and 350 cm² V^?1 s^?1 in bilayer graphene, respectively. The mobility decrease can be attributed to the resonant scattering on atomic-scale defects, likely originating from the Al precursor layer evaporated prior to sputtering.     

Surface Passivation Performance of Atomic-Layer-Deposited Al2O3 on p-type Silicon Substrates

Surface passivation performances of Al2O3 layers deposited on p-type Czochralski Si wafers by atomic layer deposition（ALD） were investigated as a function of post-deposition annealing conditions.The maximal minority carrier lifetime of 4.7 ms was obtained for AI2O3 passivated p-type Si.Surface passivation mechanisms of Al2O3 layers were investigated in terms of interfacial state density（Dit） and negative fixed charge densities（Qfix） through capacitance—voltage（C— V） characterization.High density of Qfix and low density of Dit were needed for high passivation performances,while high density of Dit and low density of Qfixdegraded the passivation performances.A low Dit was a prerequisite to benefit from the strong field effect passivation induced by high density of negative fixed charges in the Al2O3 layer.     

Influence of ZnO/graphene nanolaminate periodicity on their structural and mechanical properties

Structural, electronic and mechanical properties of ZnO/Graphene (ZnO/G) nanolaminates fabricated by low temperature atomic layer deposition (ALD) and chemical vapor deposition (CVD) were investigated. We performed scanning and transmission electron microscopy (SEM/TEM), X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-Ray photoelectron spectroscopy (XPS) and nanoindentation to characterize the ZnO/G nanolaminates. The main structural and mechanical parameters of ZnO/G nanolaminates were calculated. The obtained results were analyzed and interpreted taking into account mechanical interaction and charge effects occurring at the G-ZnO interface. The influence of graphene sublayers number on the mechanical behavior of the ZnO/G nanolaminates was studied. By reducing the bilayer thickness, the mechanical parameters of the films can be tuned (Young’s modulus 100–200 GPa, hardness 3–9 GPa). The softer response of the multilayers as compared to the single layers of ZnO and graphene was attributed to the structural changes in the ZnO layer and the interfaces. This study shows the mechanical behavior of ZnO/G nanolaminates and their influence on the development of novel electro-optical devices based on these structures.     

原子层沉积氧化铝包覆层增强五氧化二钒多孔薄膜电化学循环稳定性

最近,包覆氧化物进行表面修饰的方法已成功应用于改善锂离子电池阴极材料的容量稳定性。本文中,我们通过V2O5溶胶结合提拉法制备了V2O5多孔薄膜,并利用原子层沉积法对其包覆Al2O3原子层。V2O5多孔薄膜的电化学性质受包覆层厚度的影响,我们研究了不同薄膜厚度下的修饰效果。结果显示,原子层沉积法包覆不同厚度Al2O3原子层对锂离子电池的循环稳定性都有所改善,经10个ALD包覆循环的样品表现出最好的修饰效果。在此基础上,我们讨论探索了包覆Al2O3对容量及稳定性增强的机理。     

Al2O3添加剂对合成MgTiO3陶瓷相组成及介电性能的影响

研究了添加剂Al₂O₃对MgO和TiO_２合成MgTiO₃陶瓷烧结性、物相组成和微波介电性能的影响,XRD分析结果表明:没有添加Al₂O₃时,合成的MgTiO₃陶瓷中只含有MgTiO₃和MgTi₂O₅相;加入Al₂O₃后MgTiO₃陶瓷中除了MgTiO₃和MgTi₂O₅相外,还出现了MgAl₂O₄相,这是由于Al₂O3和 MgO发生固相反应．MgAl₂O₄的出现虽然阻碍材料的致密化并导致密度下降,但是可以降低反应烧结合成MgTiO₃陶瓷的相对介电常数和介电损耗．     

Effects of Al2O3 Particulates on the Thickness of Reaction Layer of Al2O3 Joints Brazed with Al2O3-Particulate-Contained Composite Filler Materials

In order to understand the rate-controlling process for the interracial layer growth of brazing joints brazed with active composite filler materials, the thickness of brazing joints brazed with conventional active filler metal and active composite filler materials with different volume fraction of AI203 particulate was studied. The experimental results indicate although there are Al2O3 particulates added into active filler metals, the time dependence of interracial layer growth is t^2 as described by Fickian law for the joints brazed with conventional active filler metal. It also shows that the key factor affecting the interracial layer growth is the volume fraction of alumina in the composite filler material compared with the titanium weight fraction in the filler material.     

硅片表面原子层沉积Al_2O_3薄膜及其长期腐蚀行为

目前,对硅基材表面利用原子层沉积技术(ALD)制备的Al_2O_3薄膜的耐蚀性鲜见研究报道。利用ALD技术在硅片表面制备非晶Al_2O_3薄膜。采用扫描电镜(SEM)观察薄膜的表面及截面形貌;采用X射线光电子能谱仪(XPS)分析薄膜的价键结构;通过交流阻抗谱和动电位极化曲线研究硅基材与薄膜在不同浸泡时间下的耐腐蚀性能;采用光学显微镜观察腐蚀过程中基材与薄膜的表面形貌。结果表明:ALD非晶态Al_2O_3薄膜具有致密结构,在浸泡过程中,镀膜基材比裸基材具有更好的耐腐蚀性能;且在长期浸泡情况下,Al_2O_3薄膜对基材仍能起到良好的保护作用。     

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2O3 for Enhanced CO2 Capture Performance

CO₂ capture and storage is a promising concept to reduce anthropogenic CO₂ emissions. The most established technology for capturing CO₂ relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high‐temperature CO₂ sorbent can significantly reduce the costs of CO₂ capture. A serious disadvantage of CaO derived from earth‐abundant precursors, e.g., limestone, is the rapid, sintering‐induced decay of its cyclic CO₂ uptake. Here, a template‐assisted hydrothermal approach to develop CaO‐based sorbents exhibiting a very high and cyclically stable CO₂ uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al₂O₃ (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO₂ capture and release, and (iii) a minimal quantity of Al₂O₃ for structural stabilization, thus maximizing the fraction of CO₂‐capture‐active CaO.     

Low-Loss Optical Waveguides for the Near Ultra-Violet and Visible Spectral Regions with Al(2)O(3) Thin Films from Atomic Layer Deposition

In this work, we report low-loss single-mode integrated optical waveguides in the near ultra-violet and visible spectral regions with aluminum oxide (Al₂O₃) films using an atomic layer deposition (ALD) process. Alumina films were deposited on glass and fused silica substrates by the ALD process at substrate/chamber temperatures of 200 °C and 300 °C. Transmission spectra and waveguide measurements were performed in our alumina films with thicknesses in the range of 210-380 nm for the optical characterization. Those measurements allowed us to determine the optical constants (n_w and k_w), propagation loss, and thickness of the alumina films. The experimental results from the applied techniques show good agreement and demonstrate a low-loss optical waveguide. Our alumina thin-film waveguides are well transparent in the whole visible spectral region and also in an important region of the UV; the measured propagation loss is below 4 dB/cm down to a wavelength as short as 250 nm. The low propagation loss of these alumina guiding films, in particular in the near ultra-violet region which lacks materials with high optical performance, is extremely useful for several integrated optic applications.     

Electrical and materials properties of AlN/ HfO2 high-k stack with a metal gate

In this study, aluminum nitride (AlN) was grown by molecular layer deposition on HfO₂ that had been deposited on 200 mm Si (100) substrates. The AlN was grown on HfO₂ using sequential exposures of trimethyl-aluminum and ammonia (NH₃) in a batch vertical furnace. Excellent thickness uniformity on test wafers from the top of the furnace to the bottom of the furnace (across the furnace load) was obtained. The equivalent oxide thickness was 16.5-18.8 Å for the AlN/HfO₂ stack on patterned device wafers with a molybdenum oxynitride metal gate with leakage current densities from low 10^− 5 to mid 10^− 6 A/cm² at threshold voltage minus one volt. There was no change in the work function with the AlN cap on HfO₂ with the MoN metal gate, even with a 1000 °C anneal.     

Improved properties of Pt-HfO2 gate insulator-ZnO semiconductor thin film structure by annealing of ZnO layer

Metal-insulator-semiconductor capacitors were fabricated with sputtered ZnO and atomic layer deposited HfO₂ as the semiconductor and gate dielectric layers, respectively. From the capacitance-voltage measurements, it was confirmed that pre-deposition annealing of the sputtered ZnO layer at 300 °C in air greatly decreased the interfacial trap density (∼ 2 × 10¹² cm^− 2 eV^− 1). X-ray photoelectron spectroscopy showed a decrease in the OH bonds adsorbed on the ZnO surface after pre-deposition annealing, which improved the interface property. A very small capacitance equivalent thickness of 1.3 nm was achieved, which decreased the operation voltage (< 5 V) of the device significantly.     

High resolution Rutherford Backscattering Spectrometry investigations of ZrO2 layer growth in the initial stage on native silicon oxide and titanium nitride

High Resolution Rutherford Backscattering Spectrometry (HR-RBS) with a depth resolution of about 0.3 nm near the surface was used to analyse the interface between ultrathin high-k ZrO₂-layers and the substrate. In order to improve the quality of the analysis, a method was developed that takes local thickness variations, obtained by atomic force microscopy, into account during simulation of the HR-RBS spectra. The initial stages of atomic layer deposition (ALD) growth processes on Si(100) covered with native silicon oxide (SiO₂) or with TiN have been studied. In the first case the interface is sharp, except for a small intermediate ZrSiO₄-layer, and no diffusion of Zr-atoms in SiO₂ could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO₂ on TiN. In addition, measurements of the surface topography of the TiN-layer revealed non-negligible surface roughness. Diffusion of Zr into polycrystalline TiN was demonstrated after correction for surface roughness. This observation indicates that already during the first ALD reaction cycle a small proportion of the deposited Zr-atoms diffuses - probably along grain boundaries - into the TiN-layer up to a depth of 3 nm.     

Atomic layer deposition of palladium films on Al2O3 surfaces

We examined the atomic layer deposition (ALD) of Pd films using sequential exposures of Pd(II) hexafluoroacetylacetonate (Pd(hfac)₂) and formalin and discovered that formalin enables the efficient nucleation of Pd ALD on Al₂O₃. In situ quartz crystal microbalance measurements revealed that the Pd nucleation is hampered by the relatively slow reaction of the adsorbed Pd(hfac)₂ species, but is accelerated using larger initial Pd(hfac)₂ and formalin exposures. Pd nucleation proceeds via coalescence of islands and leaves hfac contamination at the Al₂O₃ interface. Pd films were deposited on the thermal oxide of silicon, glass and mesoporous anodic alumina following the ALD of a thin Al₂O₃ seed layer and analyzed using a variety of techniques. We measured a Pd ALD growth rate of 0.2 Å/cycle following a nucleation period of slower growth. The deposited films are cubic Pd with a roughness of 4.2 nm and a resistivity of 11 μΩ cm at 42 nm thickness. Using this method, Pd deposits conformally on the inside of mesoporous anodic alumina membranes with aspect ratio ∼1500 yielding promising hydrogen sensors.     

MgO/Eu2O3共掺杂对Al2O3陶瓷微波介电性能的影响

利用湿化学法制备了MgO/Eu₂O₃共掺Al₂O₃陶瓷, 研究了不同的MgO/Eu₂O₃掺杂量对Al₂O₃陶瓷物相组成、显微结构和微波介电性能的影响。结果表明: 适量的MgO/Eu₂O₃共掺有助于Al₂O₃的致密化和晶粒生长。在介电性能方面, MgO/Eu₂O₃共掺对Al₂O₃陶瓷的介电常数没有明显的影响, 但对介电损耗的影响显著。随着Eu₂O₃含量的增加, Al₂O₃陶瓷的Q×f值会呈现先增加后下降的变化趋势。0.05wt% MgO/0.10wt% Eu₂O₃共掺的样品在1590℃下保温4 h获得的微波介电性能最佳, ε_r~9.82, Q×f ~225, 225 GHz。Q×f值的这种变化可能与样品微观结构的变化相关。先是随着MgO/Eu₂O₃共掺量的增加, 晶粒尺寸不断增加, 晶界不断减少, 这有利于Q×f值的提高; 接着, 当MgO/Eu₂O₃共掺量进一步增加时, 晶粒尺寸不断下降, 晶界增多, 这会导致样品Q×f值的降低。另外, 应力和第二相也可能对Q×f值的变化产生影响。     

Growth of aligned carbon nanotubes on ALD-Al2O3 coated silicon and quartz substrates

The smooth surface of the amorphous Al₂O₃ film on either silicon or quartz, coated by atomic layer deposition (ALD), was changed to rough surface by annealing in either air or hydrogen at high temperature (745°C) due to the formation of nanosized pinholes and micrometre pimples during the crystallisation of the amorphous Al₂O₃. The rough surface makes the growth of long carbon nanotubes (CNTs) by chemical vapour deposition impossible. Nevertheless, we were able to develop new catalyst recipes for successful growth of vertically aligned CNTs on ALD-Al₂O₃ coated silicon and quartz substrates. The lengths of the CNTs reached 90?µm on silicon substrates and 180?µm on quartz substrates. Furthermore, it is observed that the adhesion of CNTs on silicon substrates is much stronger than that on quartz substrates.     

Al2O3保护层对高温下Pt/ZnO/Al2O3电极导电稳定性的影响

本工作研究了Al₂O₃保护层的厚度对高温下声表面波器件电极导电稳定性的影响, 采用激光分子束外延方法在Pt/ZnO/Al₂O₃电极上制备了不同厚度的Al₂O₃保护层。通过测量样品高温环境中的实时电阻, 发现Al₂O₃缓冲层的厚度对电极在高温下的导电稳定性的影响非常大。结果表明, 没有Al₂O₃保护层时, Pt/ZnO/Al₂O₃电极的电阻升温至800 ℃时开始急剧地增加。当包覆40 nm的Al₂O₃保护层时, 电极在升温至900 ℃以上才出现电阻值剧烈增加的现象。而随着Al₂O₃保护层厚度的增加, 电极的电阻在高温下的导电性能也更加稳定。SEM测试结果表明, 经过1000 ℃、1 h的高温测试后, Al₂O₃保护层越薄的Pt/ZnO/Al₂O₃电极, 结块形成的Pt颗粒越大与不连续的Pt空洞更多。这些结果为制备高温下稳定工作的声表面波器件提供了一条新的思路。     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

Fabrication and interaction mechanism of Ni-encapsulated ZrO2-toughened Al2O3 powders reinforced high manganese steel composites

In order to solve the cast-infiltration difficulty and low interface bonding strength of ZrO₂-toughened Al₂O₃ (ZTA) powders reinforced high manganese steel (HMS) matrix composite, uniform and continuous Ni-encapsulated ZTA powders (ZTA_p@Ni) as reinforced phase are fabricated by electroless deposition assisted with ionic liquid additive. The effects of Ethaline concentration, temperature, ZTA concentration and deposition times on the morphology of ZTA_p@Ni have been investigated. Experimental results show that the thickness of Ni coating is about 7–10 μm, and there is no casting crack or shrink on the composite, so compact bonding between ceramic and matrix is obtained. In addition, the impact abrasive wear resistance testing demonstrates that the performance of ZTA_p@Ni reinforced HMS composite is superior to that of matrix. On the basis of experimental analysis, a schematic illustration of the cast-infiltration process is put forward. It implies that Ni-encapsulated ZTA can be wetted with molten HMS matrix to form a ZTA/Al₂NiO₄-Al₂MnO₄/Fe interface layer through Ni diffusion and reactive wetting. The interdiffusion of Ni and other elements at ZTA interface layer can reinforce the interfacial bonding strength to form an interface layer between metal and hard phases.     

Nanoarchitectured LiMn2O4/Graphene/ZnO Composites as Electrodes for Lithium Ion Batteries

LiMn2O4 nanoparticles are facilely synthesized using a sol-gel processing method. Graphene is added to LiMn2O4 electrode aiming at increasing specific capacity and improving rate capability. In order to further improve cycling stability of LiMn2O4/graphene electrode, atomic layer deposition （ALD） is used to deposit ultrathin ZnO coating composed of six ZnO ALD layers and modify the surface of either LiMn2O4/graphene electrode or individual LiMn2O4 particles to form nanoarchitectured LiMn2O4/graphene/ZnO electrodes. Both ZnO-ALD-modified LiMn2O4/graphene electrodes demonstrate enhanced cycling performance at 1C, retaining the final discharge capacity above 122 mA h g 1 after 100 electrochemical cycles, which is higher than 115 mA h g-1 of pristine LiMn2O4/graphene electrode and 109 mA h g-1 of bare LiMn2O4 electrode. The improved electrochemical performance of nanoarchitectured LiMn2O4/graphene/ZnO electrodes can be attributed to the cooperative effects from high electronic conductivity of graphene sheets to facilitate electron transportation and effective protection of ZnO ALD coating to restrict Mn dissolution and electrolyte decomposition.