不同气氛保护下退火制备的CuO/SiO2复合薄膜微观结构分析

采用射频磁控共溅射法在Si(111)衬底上沉积Cu/SiO2复合薄膜.然后在N2和NH3保护下高温退火,再于空气中自然冷却氧化,制备出CuO结构,并对其微观结构进行分析.N2保护下退火温度为1100℃时样品中主晶相为立方晶系的CuO(200)晶面,薄膜样品表面出现纳米线状结构,表面组分主要包括Cu,O元素,冷却氧化形成CuO/SiO2复合薄膜.NH3气氛保护下退火,随着退火温度的升高,CuO由单斜晶相逐渐转变为立方晶相,CuO薄膜结晶质量提高.样品于900℃和1100℃退火后,形成有序散落的微米级颗粒,前者由粒状团簇组成,颗粒表面比较粗糙;后者由片融状小颗粒融合而成,颗粒表面比较光滑.     

不同气氛保护下退火制备的CuO/SiO2复合薄膜微观结构分析

采用射频磁控共溅射法在Si (111)衬底上沉积Cu/SiO2 复合薄膜,然后在N2和NH3保护下高温退火,再于空气中自然冷却氧化,制备出CuO结构,并对其微观结构进行分析. N2保护下退火温度为1100℃时样品中主晶相为立方晶系的CuO (200）晶面,薄膜样品表面出现纳米线状结构,表面组分主要包括Cu,O元素,冷却氧化形成CuO/SiO2复合薄膜. NH3气氛保护下退火,随着退火温度的升高,CuO由单斜晶相逐渐转变为立方晶相,CuO薄膜结晶质量提高. 样品于900℃和1100℃退火后,形成有序散落的微米级颗粒,前者由粒状团簇组成,颗粒表面比较粗糙;后者由片融状小颗粒融合而成,颗粒表面比较光滑.     

CuO纳米线中的取向畴

通过简单的热氧化法,可以得到不同取向畴的CuO纳米线结构.利用群论的知识,从理论上推导出CuO纳米线中存在11种畴壁结构,其中5种已经被实验证实.同时,在800℃下得到直径较大的CuO纳米线,利用透射电子显微学相关技术分析发现,这种纳米线中存在一种新的畴壁结构,而且也属于理论上得到的11种畴壁之一.本文利用群论分析,解释了CuO纳米线中取向畴结构的生成机制,对调控CuO纳米材料的生长具有指导作用.     

退火温度对ZnO纳米线阵列形貌、结构和光学特性的影响

为获得高质量的良好取向和低成本的ZnO纳米 线阵列,利用化学浴沉积法,在石英玻 璃基底上制备ZnO纳米线阵列,在Ar气气氛中对ZnO纳米线阵列分别进行400和800℃的退火 1h处理,利用场发射扫描电子显微镜(FESEM)、X射线衍射仪(XRD)、紫外-可见分光光度 计和荧光光谱仪 分别研究了它们的形貌、晶相结构和光学特性。结果显示,退火处理后,ZnO纳米线平均直 径有所增加, ℃退火后,相邻ZnO纳米线产生粘结。随着退火温度增加,Z nO纳米线阵列的结晶质量逐渐提高,退 火至600℃时,其结晶质量最佳;在可见光区的光学透过率和光学带 宽随退火温度增加而下降。未退 火和退火400℃的ZnO纳米线阵列,仅在390n m波长处附近出现一个很弱的近带边发射峰, 当退火温度在600℃以上时,近带边发射峰迅速增强,并出现一个较 弱绿色发光带。     

衬底温度对制备出CNT膜的影响

在陶瓷衬底上通过磁控溅射方法镀上金属钛层,用含铁杂质的氧化硅对钛层进行抛光,通过微波等离子体化学气相沉积（MPCVD）法在不同的温度下短时间里制备出CNT膜。利用扫描电子显微镜、拉曼光谱,X射线衍射,分析了薄膜的结构和表面形貌。仔细研究不同温度下制备的CNT膜,得出衬底温度400℃时制备的碳膜是以非晶碳为主,600℃时置备的碳膜是良好的碳纳米管膜,800℃制备的碳纳米管膜的缺陷变得很多,以碳纳米链为主。最后得出了温度对催化活性有很大影响的结论。     

氧化物缓冲层制备Si(111)基GaN纳米线

采用氧化物缓冲层,通过射频磁控溅射系统依次在n型Si(111)衬底上沉积Ga2O3/ZnO(Ga2O3/MgO)薄膜,然后将薄膜于950℃氨化合成GaN纳米结构,氨化时间为15min。采用X射线衍射(XRD)、傅里叶红外吸收谱(FTIR)和高分辨透射电镜(HRTEM)对样品的结构进行了分析,结果显示两种缓冲层下制备的样品均为六方纤锌矿单晶GaN纳米结构,且缓冲层的取向对纳米线的生长方向有很大影响;采用扫描电镜(SEM)对样品的形貌进行了测试,发现纳米线表面光滑,长度可达几十微米,表明采用氧化物缓冲层制备了高质量的GaN线。同时对GaN纳米线的生长机理进行了简单讨论。     

石墨烯上生长GaN纳米线的研究

在常压条件下采用化学气相淀积(CVD)技术在有石墨烯插入层的衬底上生长GaN纳米线,研究了生长温度、石墨烯插入层、催化剂等因素对GaN纳米线的形貌、光学特性以及结构的影响.通过扫描电子显微镜(SEM)、光致发光(PL)谱、拉曼(Raman)谱和透射电子显微镜(TEM)等表征手段对GaN纳米线的形貌、光学特性以及结构进行表征.结果表明,在1 100℃条件下,同时有石墨烯插层和催化剂的衬底表面能够获得低应力单晶GaN纳米线.石墨烯、催化剂对于获得低应力单晶GaN纳米线有重要的作用.     

外延碳化硅纳米线的合成和显微结构研究

本文以硅为衬底,用热蒸发SiO粉末的方法合成了外延碳化硅(SiC)纳米线。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)等对SiC纳米线进行了电子显微学分析。实验发现,在SiC纳米线生长前,衬底上首先自发形成了一层SiC多晶膜,纳米线在这层多晶膜的某些晶粒上外延生长。在显微结构分析的基础上,本文探讨了外延生长一维纳米结构的有利条件是高的生长温度和低的生长速率。     

石墨烯上生长GaN纳米线

采用金属Ga升华法在石墨烯/蓝宝石衬底上生长了高质量GaN纳米线,研究了不同的生长条件,如NH3流量、反应时间、催化剂和缓冲层等对GaN纳米线形貌的影响,采用扫描电子显微镜(SEM)对GaN纳米线进行表征.研究发现,在适当的NH3流量且无催化剂时,衬底上可以生长出粗细均匀的GaN纳米线.反应时间为5 min时,纳米线密集分布在衬底上,表面光滑.在石墨烯/蓝宝石上预先低温生长GaN缓冲层,然后升温至1 100℃进行GaN纳米线生长,获得了具有择优取向的GaN纳米线结构.研究表明,石墨烯和缓冲层对获得GaN纳米线结构有序阵列具有重要的作用.     

GaN纳米线生长的影响因素与机理分析

基于气液固(VLS)反应机制,采用厚度为2~3 nm的金属镍作为催化剂,金属镓和氨气分别用作Ⅲ族和Ⅴ族的生长源,在自行改造的化学气相沉积(CVD)设备内获得了大面积GaN纳米线。通过扫描电镜(SEM)、能量分散X射线荧光(EDX)谱和透射电镜(TEM)测试,表明GaN纳米线的成核及生长与反应室气路结构有密切关系,水平弯管式气路将有利于GaN纳米线的生长。此外,生长气流将直接影响GaN纳米线的生长状况,生长温度为920℃、NH3和N2的气流量分别为100和500 cm3/min时,可以获得形貌较好的纳米线。同时,探索了Ga源与样品位置间的距离对纳米线中Ga和N的质量分数的影响,并分析了其影响机理。     

Atomic‐Scale Mechanism of Unidirectional Oxide Growth

A fundamental knowledge of the unidirectional growth mechanisms is required for precise control on size, shape, and thereby functionalities of nanostructures. The oxidation of many metals results in oxide nanowire growth with a bicrystal grain boundary along the axial direction. Using transmission electron microscopy that spatially and temporally resolves CuO nanowire growth during the oxidation of copper, herein, direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion is provided. Based on atomic scale observations of the upward growth at the nanowire tip, oscillatory downward growth of atomic layers on the nanowire sidewall and the parabolic kinetics of lengthening, it is shown that bicrystal grain boundary diffusion is the mechanism by which Cu ions are delivered from the nanowire root to the tip. Together with density‐functional theory calculations, it is further shown that the asymmetry in the corner‐crossing barriers promotes the unidirectional oxide growth by hindering the transport of Cu ions from the nanowire tip to the sidewall facets. The broader applicability of these results in manipulating the growth of nanostructured oxides by controlling the bicrystal grain boundary structure that favors anisotropic diffusion for unidirectional, 1D crystal growth for nanowires or isotropic diffusion for 2D platelet growth is expected.     

Nondestructive Characterization of Graphene Defects

An effective method is reported for oxidizing graphene/copper film in which air oxidation of the underlying copper film occurs through the grain boundary lines of graphene without oxidizing graphene. This oxidation is realized by partially immersing the graphene/copper film in sodium chloride solution. Electrons generated during etching of the graphene/copper film in electrolyte diffuse into the film in contact with air, which eventually enhances air oxidation of copper through the graphene layer. While the graphene layer acts as a protective layer against oxidation of the copper film, oxidation of the underlying Cu film near graphene grain boundary lines is observed by optical microscopy. This observation could be attributed to the selective diffusion of oxygen radicals through isolated defects and graphene grain boundaries. The process involves no appreciable oxidation of the graphene layer including the graphene grain boundary, as confirmed by use of detailed Raman and X‐ray photoelectron spectroscopy.     

Co‐synthesis of ZnO–CuO Nanostructures by Directly Heating Brass in Air

ZnO–CuO nanostructures have been simultaneously synthesized by directly heating a CuZn alloy (brass) on a hotplate in ambient conditions. Depending on the Zn concentrations in the brasses, the dominant products transition from CuO nanowires to ZnO nanostructures. By changing the growth temperature and local Zn contents, 1D ZnO nanowires/nanoflakes, 2D ZnO nanosheets, and complicated 3D ZnO networks are obtained. Electron microscopy studies show that the as‐synthesized ZnO nanoflakes and nanosheets are single crystalline. Based on “self‐catalytic” growth, a tip‐growth mechanism for ZnO nanostructures is discussed, in which the Cu in brass plays an important role to confine the lateral growth of ZnO. Finally, the electron field emission from the ZnO–CuO hybrid systems is tested for the demonstration of potential applications.     

ULSI中Cu互连线的显微结构及可靠性

观察了ULSI中大马士革结构的Cu互连线的晶粒生长和晶体学取向.分析了线宽及退火对Cu互连线显微结构及电徙动的影响.Cu互连线的晶粒尺寸随着线宽的变窄而减小.与平坦Cu膜相比,Cu互连线形成微小的晶粒和较弱的 (111) 织构.300℃、30min退火促使Cu互连线的晶粒长大、(111) 织构发展,从而提高了Cu互连线抗电徙动的能力.结果表明,Cu的扩散涉及晶界扩散与界面扩散,而对于较窄线宽的Cu互连线,界面扩散成为Cu互连线电徙动失效的主要扩散途径.     

Al/Ag/Al复合薄膜电极的抗氧化性和电性能研究

为开发大尺寸场发射显示器需要的能承受高温热处理的薄膜电极,以Al作为Ag层的保护层和与玻璃衬底的粘附层,采用直流磁控溅射制备了Al/Ag/Al复合薄膜及其电极.采用XRD、AFM、光学显微镜和电性能测试系统,研究不同温度热处理对复合薄膜和电极结构、表面形貌和电性能的影响.由于表面致密的Al2O3膜的保护,使得加热退火(<600℃)不会对Al/Ag/Al薄膜和电极造成明显的氧化,然而Al层与Ag层发生的界面扩散和固相反应增大了电极的电阻率(从5.0×10~(-8) Ω·m 上升至23.6×10~(-8) Ω·m).另外热处理温度足够高时(500℃、600℃),Ag原子向表面的扩散一定程度上降低了电极的化学稳定性.尽管如此,与Cr/Cu/Cr薄膜电极相比Al/Ag/Al薄膜电极仍然是一种能够承受高温热处理并且保持较低电阻率的新型电极.     

Phase field simulations of intermetallic compound growth during soldering reactions

Phase field simulations of the microstructural evolution of the intermetallic compound (IMC) layer formed during isothermal soldering reactions between Sn-Cu solder alloys and a Cu substrate are presented. The simulation accounts for the fast grain boundary (GB) diffusion in the IMC layer, the concurrent IMC grain coarsening along with the IMC layer growth, and the dissolution of Cu from the substrate and IMC layer. The simulation results support the previous suggestions that the growth kinetics of the IMC layer during soldering is predominantly governed by the fast GB diffusion and the concurrent coarsening rate of the IMC grains. The IMC grain coarsening is initiated by a competitive growth of the IMC grains at the solder/IMC interface. It is also shown that the dissolution of Cu into an unsaturated solder reduces the coarsening rate of the IMC grains, consequently decreasing the temporal growth exponent of the IMC layer.     

Improving Graphene Diffusion Barriers via Stacking Multiple Layers and Grain Size Engineering

It is shown that the performance of graphene diffusion barriers can be enhanced by stacking multiple layers of graphene and increasing grain size. The focus is on large‐area barriers of graphene grown by chemical vapor deposition (CVD) in the context of passivating an underlying Cu substrate from oxidation in air at 200 °C and use imaging Raman spectroscopy as a tool to temporally and spatially map the barrier performance and to guide barrier design. At 200 °C in air, Cu oxidation proceeds in multiple regimes: first slowly via transport through atomic‐scale grain boundary defects inherent to CVD‐graphene and then more rapidly as the graphene itself degrades and new defects are formed. In the initial regime, the graphene passivates better than previously reported. Whereas oxidation through single sheets primarily occurs through grain boundaries, oxidation through multiple sheets is spatially confined to their intersection. Performance further increases with grain‐size. The degradation of the graphene itself at 200 °C ultimately limits high temperature but suggests superior low temperature barrier performance. This study is expected to improve the understanding of mass transport through CVD‐graphene materials and lead to improved large area graphene materials for barrier applications.     

The effects of boron in the Cu(B)/Ti/SiO<Subscript>2</Subscript> system on the Cu-Ti reaction,resistivity, and diffusion barrier properties

The behavior of boron in Cu(4.8at.%B)/Ti/SiO₂ was investigated as a function of temperature, and its influences on the Cu-Ti interaction, resistivity, and diffusion barrier properties were also studied. The results showed the formation of a titanium boride layer at the Cu-Ti interface, after heating the Cu(B)/Ti/SiO₂ at 400°C and higher, effectively served as a barrier for the Cu and Ti diffusion, and significantly enhanced the Cu (111) texture. The resistivity dropped from 16.3 to 2.33 μΩ-cm after heating at 600°C, and continued to decrease up to 800°C. As a result, the Cu, in the form of B(O)_x/Cu/TiB₂/Ti(O)_x/SiO₂ multilayers, obtained by heating the Cu(B)/Ti/SiO₂, showed high thermal stability with low resistivity and, thus, can be used as interconnections in advanced integrated circuits. Since the Cu, in the form of B(O)_x/Cu/TiB₂/Ti(O)_x/SiO₂ multilayers, obtained by heating the Cu(B)/Ti/SiO₂, showed high thermal stability with low resistivity, it can be used as interconnections in advanced integrated circuits.     

Kinetics of Reactive Diffusion in the (Pd-Cu)/Sn System at Solid-State Temperatures

The kinetics of solid-state reactive diffusion in the (Pd-Cu)/Sn system was experimentally observed to examine how adding Cu into Pd influenced the growth behavior of compounds at the junction between the Sn-base solder and the multilayer Pd/Ni/Cu conductor during energization heating. In our experiment, Sn/(Pd-Cu)/Sn diffusion couples with Cu mole fractions (y) of 0.243, 0.497, and 0.735 were isothermally annealed at temperatures of 433 K to 473 K for various times up to 385 h. Annealing caused an intermetallic layer of rather uniform thickness to form between the Sn and Pd-Cu specimens in the diffusion couple. The intermetallic layer consisted of PdSn₄, PdSn₃, PdSn₂, and Cu₆Sn₅ for y = 0. 243. However, PdSn₃ and PdSn₂ were not clearly detected for y = 0.497 or 0.735. The total thickness of the intermetallic layer was proportional to a power function of the annealing time, with the exponent of the power function being 0.33 to 0.53. Cases where the exponent was smaller than 0.5 indicated that boundary diffusion controlled the growth of the intermetallic layer. Cases where the exponent was equal to 0.5 implied that volume diffusion was the rate-controlling process. Even for exponents close to 0.5, however, the grain growth behavior of the intermetallic layer suggested that the layer growth was governed by boundary diffusion. For the annealing times tested in this work, the overall growth rate of the intermetallic layer was insensitive to the Cu concentration at y < 0.75, but decreased remarkably with increasing Cu concentration at y > 0.75. As a consequence, the growth of compounds at the Pd junction in the multilayer Pd/Ni/Cu conductor was markedly decelerated by adding Cu when y > 0.75.