Abnormal grain growth in copper films during magnetically enhanced plasma processing

The kinetics of grain growth in thin copper films during magnetically enhanced (ME) plasma processing is monitored. Transmission electron microscopy (TEM) results suggest microstructural evolution characteristic of abnormal grain growth in these films. The kinetics of abnormal grain growth appears to depend on gas pressure in the reactor.     

Room temperature grain growth in electroplated copper thin films

The microstructural changes in copper thin films at room temperature after electrolytic deposition have been studied by X-ray diffraction, wafer curvature stress measurement, electrical resistance measurement, and local orientation mapping. Changes in texture and stress were found to take place earlier than grain growth became distinctly visible. Additionally, FIB cross sections showed the evolution of grains in third dimension. The results are discussed in terms of grain growth from the bottom to the top of the film.     

Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin‐Film Electrodes on YSZ Electrolyte

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

Thin‐Film Electrodes: Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin Film Electrodes on YSZ Electrolyte (Adv. Funct. Mater. 3/2011)

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

Growth and Properties of Hybrid Organic‐Inorganic Metalcone Films Using Molecular Layer Deposition Techniques

Molecular layer deposition (MLD) is a useful technique for fabricating hybrid organic‐inorganic thin films. MLD allows for the growth of ultrathin and conformal films using sequential, self‐limiting reactions. This article focuses on the MLD of hybrid organic‐inorganic films grown using metal precursors and various organic alcohols that yield metal alkoxide films. This family of metal alkoxides can be described as “metalcones”. Many metalcones are possible, such as the “alucones” and “zincones” based on the reaction of trimethylaluminum and diethylzinc, respectively, with various organic diols such as ethylene glycol. Alloys of the various metalcones with their parent metal oxide atomic layer deposition (ALD) films can also be fabricated that have an organic‐inorganic composition that can be adjusted by controlling the relative number of ALD and MLD cycles. These metalcone alloys have tunable chemical, optical, mechanical, and electrical properties that may be useful for designing various functional films. The metalcone hybrid organic‐inorganic materials offer a new tool set for engineering thin film properties.     

基于PECVD的SiO2薄膜制备研究进展

二氧化硅(SiO₂)薄膜因其卓越的光学性能,在半导体器件、集成电路、光学涂层等领域具有巨大的应用潜力。然而,SiO₂薄膜制备过程中面临表面粗糙度、杂质控制和致密性等问题。为解决这些问题,研究者们通过工艺改进和表面修饰等手段来提高SiO₂薄膜的性能。在众多SiO₂薄膜制备技术中,等离子体增强化学气相沉积(Plasma-Enhanced Chemical Vapor Deposition, PECVD)技术由于沉积SiO₂薄膜所需温度低、原位生长等优势,成为制备SiO₂薄膜最常用的方法。综述了用PECVD技术制备SiO₂薄膜的发展历程,并探讨了关键工艺参数和后处理工艺对薄膜质量的影响。对PECVD技术的深入研究,有助于实现对SiO₂薄膜生长的更精准控制,进一步拓展其广泛的应用前景。     

Microstructures of YSZ and CGO Thin Films Deposited by Spray Pyrolysis: Influence of Processing Parameters on the Porosity

Microstructures of yttria‐stabilized zirconia (YSZ) thin films deposited by spray pyrolysis at 370 °C on sapphire are investigated. The as‐deposited films are predominantly amorphous and crystallize upon heating at temperatures above 370 °C, developing grains in the range of 5 nm to several 100 nm. During post‐deposition heat treatment up to 800 °C, ～ 50 vol% porosity develops in the center of the films with gradients towards almost dense interfaces to the air and substrate. The reason for this porosity is the decomposition of residues from the precursor and the free volume liberated due to crystallization. Dense YSZ thin films consisting of one monolayer of grains are obtained with annealing temperatures exceeding 1200 °C. In gadolinium‐doped‐ceria (CGO) thin films similar microstructures and porosity are found after low‐temperature heat treatments indicating that the precursor residues due to the deposition method are the main cause of the porosity. Grain growth stagnation in annealed thin films is observed in both the YSZ and in CGO thin films. Stagnating grain growth in the thin films is rather caused by reduced grain boundary mobility, here predominately due to a “secondary phase”, i.e., pores, than to other effects. The stagnation ceases at higher annealing temperatures after densification has taken place.     

Growth Front Evolution of GaN Thin Films on Sapphire Substrate During HVPE

The growth front evolution of GaN thin films deposited on sapphire substrate by hydride vapor phase epitaxity has been studied with atomic force microscope. The evolution of the surface morphology presents four features of stage with the growth process. In initial growth stage, the surface is granular, and the typical grain diameter is about 250nm for t =0.1min. 3D growth plays a key role before the films come up to full coalescence, which causes a rough surface. After 0.1min the growth dimension decreases with the increase of lateral over growth, the surface roughness obviously decreases. From 0.4min to 3min, the growth front roughness increases gradually, and the evolution of the surface roughness exhibits the characteristics of self-affined fractal. Beyond 3min, the root-mean-square decreases gradually, which means the deposition behavior from hyper-2D growth gradually turns into layer growth mode with the increase of growth time.     

Single‐Crystal Germanium Growth on Amorphous Silicon

Growing single‐crystal semiconductors directly on an amorphous substrate without epitaxy or wafer bonding has long been a significant fundamental challenge in materials science. Such technology is especially important for semiconductor devices that require cost‐effective, high‐throughput fabrication, including thin‐film solar cells and transistors on glass substrates as well as large‐scale active photonic circuits on Si using back‐end‐of‐line CMOS technology. This work demonstrates a CMOS‐compatible method of fabricating high‐quality germanium single crystals on amorphous silicon at low temperatures of <450 °C. Grain orientation selection by geometric confinement of polycrystalline germanium films selectively grown on amorphous silicon by chemical vapor deposition is presented, where the confinement selects the fast‐growing grains for extended growth and eventually leads to single crystalline material. Germanium crystals grown using this method exhibit (110) texture and twin‐mediated growth. A model of confined growth is developed to predict the optimal confining channel dimensions for consistent, single‐crystal growth. Germanium films grown from one‐dimensional confinement exhibit a 200% grain size increase at 1 μm film thickness compared to unconfined films, while 2D confinement growth achieved single crystal Ge. The area of single crystalline Ge on amorphous layers is only limited by the growth time. Significant enhancement in room temperature photoluminescence and reduction in residual carrier density have been achieved using confined growth, demonstrating excellent optoelectronic properties. This growth method is readily extensible to any materials system capable of selective non‐epitaxial deposition, thus allowing for the fabrication of devices from high‐quality single crystal material when only an amorphous substrate is available.     

Influence of substrate on the growth of microcrystalline silicon thin films deposited by plasma enhanced chemical vapor deposition

Microcrystalline silicon (μc-Si) thin films are widely used for silicon thin film solar cells, especially in the high performance tandem solar cells which comprise an amorphous silicon junction at the top and a μc-Si junction at the bottom. One of the major factors affecting the photovoltaic properties of μc-Si thin film solar cells of thin films is the quality of the μc-Si thin films. In this work, we investigated the effect of substrates on the crystallization characteristics and growth behaviors of μc-Si thin films grown by the plasma enhanced chemical vapor deposition method (PECVD), and found that substrates have a strong effect on the crystallization characteristics of μc-Si thin films. In addition, the growth rate of μc-Si thin films was also highly influenced by the substrates. Three types of substrates, quartz glass, single crystalline silicon and thermally oxidized single crystalline silicon, were used for growing μc-Si thin films from SiH₄/H₂ with a flow rate ratio 2:98 at different temperatures. Crystallization characteristics of these μc-Si thin films were studied by Raman scattering and X-ray diffraction techniques.     

Nanocrystalline Si:H films made by inductively coupled plasma using internal low inductance antenna

P-type hydrogenated nanocrystalline silicon (nc-Si:H) thin films are prepared on glass substrate by an inductively coupled plasma chemical vapor deposition system using multiple internal low inductance antenna units. The deposition rate as well as the microstructural and electrical properties of the nc-Si:H films are investigated systematically as functions of hydrogen dilution, discharge power and working distance. The effects of various process parameters are identified and rationalized. The applicability of this type of high density plasma to manufacture nc-Si:H films is critically assessed.     

Stress development during evaporation of Cu and Ag on silicon

This work presents results of stress measurements during deposition of thin silver and copper films on 100 μm Si substrate. The stress in thin films has been determined by means of an optical system for the measurement of sample’s curvature. This system was applied in situ in a high vacuum deposition system. For Ag films the stress occurring during deposition goes from a low compressive value to tensile for thickness less than 30 nm and to compressive above this. For Cu films we observe tensile stress for thickness less 20 nm and above 50 nm. The same general trend of stress evolution with thickness is present in all cases at initial stage. There is the same growth mode for Cu and Ag because of the similar shapes of stress curves for thickness lower than 30 nm The behavior of stress evolution was explained by island nucleation and growth, island coalescence and continuous film growth. The difference in the stress evolution above 30 nm is caused by the fact that silver may be less sensitive than copper to adsorption of impurities. Adsorbed contamination inhibits compressive stress increase generated by grain boundary and defects remaining in the film.     

Texture and microstructure of thin copper films

Microstructure is an important factor influencing the reliability of thin film interconnects. The microstructure of copper films is of particular interest because of its use in numerous electronic applications. Pole figure x-ray diffraction and transmission electron microcopy were conducted on copper films deposited by several techniques: sputtering, partially ionized beam deposition, chemical vapor deposition, evaporation, and electroplating. Quantitative texture data are determined from fiber texture plots. A typical copper film consists of three texture components: (111), (200), and random. (220) and (511) texture components are possible under some deposition conditions. Compared to aluminum films, the fraction of the random texture component and the distribution of the (hkl) components in copper films are relatively large. Bimodal grain size distributions are observed in some films.     

金刚石薄膜的分层生长

采用热丝化学气相沉积生长出优异的金刚石薄膜。研究了薄膜的分层生长过程，薄膜的层状结构及膜厚随沉积时间的变化特性。     

超高真空化学气相沉积外延生长锗硅材料及其应用

综述了硅基锗硅薄膜的外延生长技术、设备及其在光电子器件上的应用,其中着重介绍了超高真空化学气相沉积系统(UHVCVD)。目前来说,UHVCVD是产业化制备高质量锗硅材料的最佳选择。     

Chemical and morphological properties of (Ti-Zr)N thin films grown in an arc pulsed system

Due to its extensive field of application in different areas, including mechanics, electronics, tribology and optics the last decade has seen a large interest the study of titanium-zirconium-nitride (Ti-Zr)N thin films grown by different techniques. We had produced (Ti-Zr)N thin films and in this work chemical, morphological and electronics analysis are presented. Thin films were produced by the PAPVD (plasma assisted physics vapor deposition) technique, by pulsed arc in a mono-vaporizer system using a titanium-zirconium target with 99.99% purity. Argon-nitrogen mixture for the discharge was used. For the analyses X-ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM) techniques were used, XPS results shown the chemical composition of the films. Films were morphologically and tribologically characterized using SPM, obtaining grain size and friction coefficient.     

激光辅助固态薄膜淀积技术的进展

本文综述了近年来激光辅助固态薄膜淀积技术的进展。简要概述了脉冲激光蒸发淀积(PLED)和激光诱导化学气相淀积(LCVD)的基本原理、淀积系统和激光器。侧重详细介绍了这种技术在制备微电子器件所需要的高Tc超导体膜、金属膜、半导体膜和介质膜中的应用。     

Structurally Stable Manganese Alkoxide Films Grown by Hybrid Molecular Layer Deposition for Electrochemical Applications

Hybrid molecular layer deposition (MLD) has significant potential for the creation of ultrathin electrochemically active materials, due to its ability to combine organic and inorganic species to modulate film properties. However, only a limited number of hybrid MLD processes are demonstrated with electrochemically relevant elements, such as manganese. Here, a “manganicone” manganese hybrid MLD chemistry is developed using the precursors bis(ethylcyclopentadienyl)manganese and ethylene glycol. The resulting manganese alkoxide coordination networks are shown to have many interesting properties, including the ability to seamlessly fill high aspect ratio vias and the chemical conversion into manganese carboxylate in air over several hours at room temperature. Linear, self‐saturating growth is reported. Importantly, hybrid manganicone films annealed to 480 °C in air demonstrate a greater stability to restructuring during electrochemical testing than their inorganic counterparts grown by atomic layer deposition, without reducing the activity of the reactive sites on the manganese surface. Thus, hybrid manganese films grown by MLD have significant promise for use as catalysts for the oxygen evolution reaction and as electrodes in thin film batteries.     

Effect of the underlayer on the microstructure and surface evolution in Al-0.5wt.%Cu polycrystalline thin films

The effects of the Ti underlayer on the evolution of grain morphology, crystallographic texture, and surface roughness of Al-0.5wt.%Cu thin films during sputter deposition have been characterized. In comparison to SiO₂ substrates, Ti underlayers reduce the AlCu thickness at which film continuity is reached, reduce the AlCu columnar grain size, and allow exact Al (111) fiber texture development. The AlCu films on both Ti and SiO₂ are primarily randomly oriented at early stages of deposition. A near-(111) Al fiber texture in AlCu/SiO₂ films initiates during the preferential growth of ≈5° offset islands prior to film continuity, seeding the near Al (111) texture as film continuity is reached. The exact Al (111) fiber orientation in AlCu/Ti films develops after film continuity. The near-(111) and exact (111) fiber textures strengthen with further deposition due to combined normal and abnormal grain growth. Film coalescence and grain growth lead to a significant smoothing effect during the early stages of deposition.