Atomic layer deposition ultra-barriers for electronic applications-strategies and implementation

We show that Al2O3 thin films, grown by atomic layer deposition (ALD) on polyester, are ultrabarriers with moisture permeation <10(-5) g-H2O/m2-day, as determined after aging for more than three years. We present evidence that the mechanism for gas permeation in ALD Al2O3 films is not due to pinholes, but that the onset of permeation occurs abruptly, analogous to electrical breakdown in oxide thin films. We show that the permeation onset time increases for thicker Al2O3 films and higher ALD process temperature, for which the hydrogen defect concentration in Al2O3 films is less. Further, we show that mild plasma treatment of the polyester, prior to ALD deposition of Al2O3, makes the surface more hydrophilic and reduces moisture permeation compared to an untreated surface. Similarly, ALD deposition on the bare or non-slip side of the polyester film is preferred for low permeation.     

Infrared and raman spectroscopic studies of optically transparent zirconia (ZrO2) films deposited by plasma-assisted reactive pulsed laser deposition

Plasma-assisted pulsed laser deposited zirconia (ZrO(2)) films were studied by Fourier transform infrared (FT-IR) and Raman spectroscopy for structural characterization and thermal stability in combination with optical characterization by spectroscopic ellipsometry and optical transmission measurements. Only the monoclinic ZrO(2) phase was positively identified from the infrared and Raman spectra of the as-deposited ZrO(2) films, which show excellent optical transparency from the ultraviolet to the near infrared as revealed by optical characterization. The as-deposited ZrO(2) films are free of any SiO(x) interfacial layer when deposited on silicon. The prepared ZrO(2) films exhibit good thermal stability in their structural, optical, and interfacial properties up to 900 °C. Upon annealing above 1100 °C, a silicon oxide interfacial layer forms due to the oxidation of the silicon substrate surface by the oxygen diffused from the oxide film to the silicon substrate at high temperatures.     

低毒单体DMAA用于ZrO2/Al2O3坯体注凝成型

采用低毒的单体N, N-二甲基丙烯酰胺(DMAA)制备了氧化锆增韧氧化铝(ZrO₂/Al₂O₃)坯体。讨论了分散剂的用量、 ZrO₂/Al₂O₃浆料的pH值、 粉体中ZrO₂含量、 粉体所占浆料的固相体积分数、 球磨时间、 预混液中DMAA的浓度(质量分数)对ZrO₂/Al₂O₃浆料黏度的影响。并研究了注凝成型ZrO₂/Al₂O₃坯体的性能和显微结构。结果表明, 当浆料pH值为9, 分散剂的添加量为ZrO₂/Al₂O₃粉体质量的0.6%, 球磨时间为6 h, ZrO₂/Al₂O₃浆料具有最小的黏度。固相体积分数的提高和DMAA加入量的增大都会提高ZrO₂/Al₂O₃浆料的黏度, ZrO₂的加入会降低浆料的黏度。用DMAA制备得到的ZrO₂/Al₂O₃坯体结构均匀, 抗弯强度达到25 MPa。      

透明导电膜ZnO:Al(ZAO)的组织结构与特性

ZnO:Al(ZAO)是一种简单并半导体氧化物薄膜材料，具有高的载流子浓度和光学禁带宽度，因而具有优异的电学和光学性能，极具应用价值，对于其能级高度简并的ZAO半导体薄膜材料，在较低的温度下，离化杂质散射占主导地位，在较高的温度下，晶格振动散射将成为主要的散射机制；晶界散射仅当晶粒尺寸较小（与电子的平均自由程相当）时才起作用，本文分析了ZAO薄膜的制备方法，晶体结构特性，电子和光学性能以及载流子的散射机制。     

Enhanced electrochemical performance of Li-rich manganese layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 by surface modification with Al2O3–ZrO2 for lithium-ion battery

Journal of Materials Science: Materials in Electronics - In this work, the Li-rich manganese layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 (LMNC in short) is coated with a novel Al2O3–ZrO2 layer...     

Joining of Zirconia and Ti-6Al-4V Using a Ti-based Amorphous Filler

Polycrystalline ZrO2-3 mol.%Y2O3 was brazed to Ti-6Al-4V by using a Ti47Zr28Cu14Ni11(at.%) amorphous ribbon at 1123-1273 K in a high vacuum. The influences of brazing temperature on the microstructure and shear strength of the joints were investigated. The interfacial microstructures can be described as ZrO2/TiO+TiO2+Cu2Ti4O+Ni2Ti4O/α-Ti+(Ti,Zr)2(Cu,Ni) eutectic/acicular Widmanst¨aten structure/Ti-6Al-4V alloy. With the increase in the brazing temperature, the thickness of the TiO+TiO2+Cu2Ti4O+Ni2Ti4O layer reduced, the content of the α-Ti+(Ti,Zr)2(Cu,Ni) eutectic phase decreased, while that of the coarse α-Ti phase gradually increased. The shear strength of the joints did not show a close relationship with the thickness of the TiO+TiO2+Cu2Ti4O+Ni2Ti4O layer. However, when the coarse (Ti,Zr)2(Cu,Ni) phase was non-uniformly distributed in the α-Ti phase, or when α-Ti solely situated at the center of the joint, forming a coarse block or even connecting into a continuous strip, the shear strength greatly decreased.     

Effects of interfacial layer on characteristics of TiN/ZrO2 structures

To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.     

拟薄水铝石凝胶制备牙科托槽用ZTA陶瓷的研究

利用拟薄水铝石的凝胶作用,以浓HNO_3为引发剂,将Al_2O_3(1μm)粉末和含3%Y_2O_3的ZrO_2(200nm)粉末均匀填充在拟薄水铝石的溶胶双电层内,在一定温度和时间下胶凝固化并干燥成坯。将生坯通过不同的温度烧结后,制备出ZTA陶瓷正畸托槽材料。主要研究拟薄水铝石的胶体行为、不同固含量下生坯的性能以及ZrO_2对陶瓷晶粒结构和力学性能的影响。结果表明,经拟薄水铝石凝胶制备的陶瓷生坯具有一定抗弯强度(达4 MPa),可用于力学加工。在该制备方法中,ZrO_2可更好地发挥增韧作用,增加陶瓷烧结后致密度,提高陶瓷托槽材料的抗弯强度。     

Al_2O_3-TiO_2-ZrO_2含纳米结构等离子喷涂层的显微硬度及韧性

为了提高传统Al_2O_3+40%TiO_2等离子喷涂层的力学性能,将纳米结构的ZrO_2粉末引入热喷涂层,采用液相喷雾造粒的方法将纳米ZrO_2-准微米级Al_2O_3/TiO_2颗粒团聚成适用于等离子喷涂的微米级粉体,并用等离子喷涂技术制备出含有纳米结构的陶瓷涂层.利用X射线衍射仪、扫描电镜和显微硬度计等对涂层的微观结构和性能进行了检测.结果表明,最佳喷涂功率40 kW下制备的纳米陶瓷涂层的显微硬度和韧性比传统涂层有了明显提高.     

纳米Al2O3的晶型对聚酰亚胺杂化薄膜性能的影响

将经偶联剂处理的纳米Al2O3粉体,借助超声波以一定方式均匀分散于聚酰胺酸溶液中,制备出Al2O3不同晶型、不同含量的PI/纳米Al2O3杂化薄膜,并对杂化薄膜微观形貌、聚集态结构、光透过率、热稳定性、电击穿场强进行研究,分析Al2O3晶型和含量对PI/纳米Al2O3杂化薄膜的结构和性能的影响.结果表明:PI/纳米Al2O3杂化薄膜的热稳定性,电击穿场强均高于纯PI薄膜,且随着纳米Al2O3含量的提高热稳定性也随之提高,电击穿场强先升高后降低;填充Al2O3粉体的晶型对PI薄膜分子链堆积密度有较大的影响,导致添加不同晶型Al2O3的杂化薄膜性能的差异.     

The effects of radio frequency plasma power on Ai2O3 films deposited at room-temperature by remote plasma atomic layer deposition

Al2O3 films were deposited by a remote plasma atomic layer deposition (RPALD) method at room temperature (25 degrees C) in a reactor using alternating exposures of Al(CH3)3 and O2 plasma. Oxygen plasma was used as a reactant gas to decompose the trimethylaluminum [TMA, Al(CH3)3] precursor at room temperature. The RF plasma power was increased to produce enough radicals for the deposition of the Al2O3 films at room temperature. Then, changes in the interfacial and bulk properties of the deposited Al2O3 films were investigated according to increasing RF power. Al2O3 films deposited by RPALD with RF powers over 100 W showed similar bulk properties, indicating that radicals over a certain threshold did not have a decisive effect on the additional decomposition of precursors for a low impurity content in the films. An increase in RF plasma power could improve the interfacial stability due to an increase in radicals and ions in the plasma and the minimization of plasma-induced substrate damage by adopting remote plasma.     

Effect of interfacial features on the mechanical and electrical properties of rGO/Al composites

This study investigates the effect of interfacial features on the mechanical and electrical properties of reduced graphene oxide (rGO)/aluminum (Al) composites. The composites were fabricated using a hybrid process that includes chemical and mechanical methods. First, GO was uniformly dispersed on the surface of Al powder via a solution process. A strong interface was formed between GO and Al via several chemical bonds by using polyvinyl alcohol (PVA) as an organic binder during the solution process. Then, GO was thermally reduced to rGO, wherein the interfacial features were varied according to the atmosphere (vacuum or H₂(10%)/N₂(90%) mixed gas). Subsequently, rGO was mechanically embedded and further dispersed within soft Al powder through the plastic deformation of Al. Vacuum was found to be more effective than the mixed gas at removing functional groups containing oxygen in GO and therefore generated a tighter interface. As a result, the composites containing rGO that were reduced under vacuum showed higher strength and lower ductility compared with those reduced under the mixed gas. Conversely, the interfacial features rarely affected the electrical conductivity of the composites because the electrical conductivity of rGO was considerably lower than that of Al. Consequently, compared with their monolithic counterparts, the composites containing only 0.2 vol% rGO showed a 374-MPa yield strength without a significant loss of electrical conductivity, thereby demonstrating their potential feasibility in electrical and electronic applications.     

Al2O3/TiO2 multilayer passivation layers grown at low temperature for flexible organic devices

In this study, the permeability of passivation layers consisting of aluminum oxide (Al2O3) and titanium oxide (TiO2) was examined. The films were deposited on poly(ether sulfone) (PES) substrates via electron cyclotron resonance atomic layer deposition (ECR-ALD) at various deposition temperatures. The optimum plasma power and deposition temperature were investigated through measurements of the refractive index and packing density of the Al2O3 and TiO2 films. A buffer layer/multilayer structure was proposed in this study to improve the passivation barrier performance. A low water vapor transmission rate (WVTR) of approximately 5 x 10(-3) g/m2 x day was achieved with two Al2O3/TiO2 stacks with thicknesses of 40 nm deposited at 80 degrees C. Based on the Arrhenius rate equation, the activation energy of water vapor transmission through different passivation structures was examined. The activation energies of Al2O3, Al2O3/TiO2, and two Al2O3/TiO2 stacks with thicknesses of 40 nm were 51.8, 63.9, and 74.7 kJ/mol, respectively.     

Enhanced electrical characteristics of sol–gel-derived amorphous SrTiO<Subscript>3</Subscript> films

Amorphous SrTiO₃ thin films were fabricated on Pt (100)/Ti/SiO₂/Si substrates by sol–gel and spin-coating technology and their surface and cross-section morphology were characterized by using field emission scanning electron microscopy. A broad absorption band at about 3390 cm^?1 owing to the stretching vibrations of hydroxyl groups in the absorbed water was observed from fourier transform infrared spectroscopy. J–E measurements were used to investigate the electrical characteristics of SrTiO₃ films. The breakdown characteristics and leakage current are strongly dependent upon their electrode materials. SrTiO₃ films with Al top electrodes exhibit significantly higher breakdown strength and much lower leakage current than those with Au top electrodes. Moreover, samples with Al electrodes exhibit distinct electrical characteristics when a negative voltage was applied under different testing conditions. The surface chemical state of aluminum was analyzed by using X-ray photoelectron spectroscopy, indicating that the 45 nm thick Al electrode was completely transformed into aluminum oxide layer when a positive voltage was applied. These results show that the anodic oxidation of the Al electrodes and films is suggested to be responsible for the enhanced electrical characteristics of SrTiO₃ thin films.     

基于高温熔凝法Al_2O_3/ZrO_2/YAG共晶陶瓷显微组织演变规律

作为超高温结构材料,共晶氧化物陶瓷的力学性能和显微组织密切相关。采用高温熔凝法制备Al_2O_3/ZrO_2/YAG共晶陶瓷体,研究熔体温度和结晶种子对凝固组织影响规律,运用经典形核机制和Jackson-Hunt共晶生长模型探讨了凝固组织的演变机理。研究表明,随着熔体温度升高(1750~2000℃),凝固体物相组成从α-Al_2O_3,c-ZrO_2和YAG转变为α-Al_2O_3,c-ZrO_2和亚稳相YAP。凝固组织依次经历:非共晶Al_2O_3/ZrO_2/YAG、不规则共晶Al_2O_3/ZrO_2/YAG、纳米纤维状共晶Al_2O_3/ZrO_2/YAG和复杂粗大的亚稳复合陶瓷Al_2O_3/ZrO_2/YAP。分析表明,凝固组织的演变源于异质晶核点不断钝化导致形核过冷度和凝固路径改变,所以合理选择熔体温度和结晶种子是共晶组织调控的关键。     

ZrO2的加入对(CeO2)0.86(SmO1.5)0.14陶瓷性能的影响

探讨了添加 ＺｒＯ_２对 ＣｅＯ_２／Ｓｍ_２Ｏ₃体系电导率和力学性能的影响,并用 ＸＲＤ、ＳＥＭ等对材料的微观性能进行了试验分析．结果发现,添加 ＺｒＯ_２使材料的电导率降低,主要是因为ＺｒＯ_２的固清使得ＣｅＯ_２电解质材料的晶格常数减小,活化能增加造成的;添加 ＺｒＯ_２可提高材料的断裂强度,使材料断裂以穿晶断裂为主,其原因可能是ＺｒＯ_２的固溶强化了晶界;添加 ＺｒＯ_２促进了致密烧结,使晶界结合紧密．实验确定,外加 ２．５ｍｏｌ％ ＺｒＯ_２的 ＣｅＯ_２电解质具有适中的强度和电导率,可以作为电解质材料应用．     

Electromechanical Behavior of Al/Al2O3 Multilayers on Flexible Substrates: Insights from In Situ Film Stress and Resistance Measurements

A series of Al and Al/Al₂O₃ thin-film multilayer structures on flexible polymer substrates are fabricated with a unique deposition chamber combining magnetron sputtering (Al) and atomic layer deposition (ALD, Al₂O₃, nominal thickness 2.4–9.4 nm) without breaking vacuum and thoroughly characterized using transmission electron microscopy (TEM). The electromechanical behavior of the multilayers and Al reference films is investigated in tension with in situ X-ray diffraction (XRD) and four-point probe resistance measurements. All films exhibit excellent interfacial adhesion, with no delamination in the investigated strain range (12%). For the first time, an adhesion-promoting naturally forming amorphous interlayer is confirmed for thin films sputter deposited onto polymers under laboratory conditions. The evolution of Al film stresses and electrical resistance reveal changes in the deformation behavior as a function of oxide thickness. Strengthening of Al is observed with increasing oxide thickness. Significant embrittlement can be avoided for oxide layer thicknesses ≤2.4 nm.     

交流磁控溅射制备ZAO薄膜工艺参数的研究

对于交流磁控溅射氧化锌铝陶瓷靶材制备ZAO薄膜,研究了氧流量、基体温度、靶电流密度、铝的掺杂量、本底真空压力和工作气体压力对ZAO薄膜电学性能的影响规律,优化了工艺参数,为工业化生产提供了实验依据.     

Al_2O_3对全稳定ZrO_2显微组织的影响

本文利用ＳＥＭ、ＥＤＡＸ等测试手段，细致地研究了Ａｌ２Ｏ３对全稳定ＺｒＯ２显微组织的影响．研究的结果表明，Ａｌ２Ｏ３在全稳定ＺｒＯ２中主要分布于晶界及第二相粒子中，其在晶内的固溶度极低；Ａｌ２Ｏ３能显著地促进ＺｒＯ２晶粒的生长，从而使气孔难以消除，降低材料的密度．     

SiC晶须增韧Al_2O_3及ZrO_2（Y_2O_3）基陶瓷复合材料的抗热震行

采用三点弯曲及扫描电镜等方法研究了ＳｉＣｗ／Ａｌ２Ｏ３、ＳｉＣｗ／ＺｒＯ３（Ｙ２Ｏ３）及ＳｉＣｗ／Ａｌ２Ｏ３＋ＺｒＯ２（Ｙ２Ｏ３）陶瓷复合材料的抗热震性．结果表现ＳｉＣｗ的加入使Ａｌ２Ｏ３、ＺｒＯ２（Ｙ２Ｏ３）以及Ａｌ２Ｏ３＋ＺｒＯ２（Ｙ２Ｏ３）基体的抗热震性显著提高，Ａｌ２Ｏ３陶瓷基复合材料的抗热震性明显优于ＺｒＯ２（Ｙ２Ｏ３）陶瓷基复复合材料．同时发现在Ａｌ２Ｏ３十ＳｉＣｗ材料基础上再加入少量ＺｒＯ２（２Ｙ）颗粒（１０Ｖｏ１％），也可进一步提高Ａｌ２Ｏ３＋ＳｉＣｗ材料的抗热震性．