电化学沉积等表面技术在集成电路制造中的作用

集成电路制造也称芯片制造,在整个工业产业链中越来越重要,而电化学沉积(电镀)等表面技术起到非常关键的作用。介绍芯片制造中用到的电化学沉积、物理气相沉积(PVD)、化学气相沉积(CVD)、抛光等表面技术的基本情况和特点, 探讨铜互连电镀、化学机械抛光(CMP)、硅通孔(TSV)垂直互连电镀铜填充、芯片表面再布线(RDL)电镀铜工艺、键合凸点(Bump)电镀铜/锡工艺、集成电路引线框架/封装基板的电化学蚀刻工艺等,通过总结电化学沉积等表面技术的发展, 深入分析传统电镀技术在集成电路制造中的新特点,推动集成电路制造技术的进步。     

Structure of vacuum Cu–Ta condensates

The structure of vacuum condensate foils (separated from substrates) of the binary Cu–Ta system has been investigated both in the initial condensed state and after annealings at temperatures of up to 1000°С. It has been shown that the alloying of a vapor flow of the matrix metal (copper) with tantalum to ~0.5 at % makes it possible to reduce the grain size from 3 μm to 50 nm. Depending on the tantalum concentration, condensates exhibit a broad spectrum of structural states, i.e., single- and two-phase, a supersaturated solution of tantalum in the fcc lattice of copper, etc. The structure of the objects possesses a high thermal stability. The temperature of the start of grain growth in the copper matrix depends on the tantalum content and can reach 900°С. The dispersion of the structure of copper condensates and its thermal stability is due to the formation of segregates of tantalum atoms at the boundaries of grains of the copper matrix both in the process of condensation and upon subsequent annealing.     

The role of process variables in laser-based direct metal solid freeform fabrication

A fundamental understanding of how process variables relate to deposit characteristics is essential for solid freeform fabrication (SFF) process control. In this article, recent research into modeling and understanding solidification-related phenomena in laser-based direct metal SFF processes is summarized. A “process map” approach is outlined, which provides nonlinear thermomechanical model results for key deposit characteristics over the full range of relevant process variables. Process maps for predicting melt pool size, thermal gradients and maximum residual stress in thin-walled structures are presented, and process-related insights from them are described. Work underway to develop additional process maps, including those for microstructural control, is also summarized. For more information, contact Jack Beuth, Carnegie Mellon University, Department of Mechanical Engineering, 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213-3890; (412) 268-3873; fax (412) 268-3348; e-mail beuth@andrew.cmu.edu.     

Growth of conformal copper films on TaN by electrochemical deposition for ULSI interconnects

Seedless copper electrochemical deposition (ECD) becomes a potential interconnect technology while device dimension keeps shrinking in ULSI design. In seedless copper ECD on TaN, which is a widely used diffusion barrier, uniform growth of copper film on TaN is hindered because a robust native Ta₂O₅ exists on TaN surface. Complete removal of the native Ta₂O₅ can be attained using a saturated KOH solution that is assisted by an anodic voltage. This then permits that copper film grows on the pretreated TaN surface in a copper-citrate (Cu-Cit) complex electrolyte. Its growing morphology and deposition rate are dependent on the etching depth of as-deposited TaN in the KOH solution. Even for a very short etching time of 0.8 s, thin Ta₂O₅ is totally etched off and the activated TaN surface appears. Thin and conformal copper films grown in a layer-by-layer mode on the TaN surface are proper to function as an ECD seed or metal lines for ULSI interconnects.     

Interface instability in the drawing process of copper/tantalum conductors

Copper/tantalum test billets have been cold drawn, using the process developed for the elaboration of copper/niobium multifilamentary conductors, for the development of high strength and high conductivity conductors for high pulsed magnetic fields. After a section reduction of 60%, a macroscopic roughness of the tantalum surface has been observed: two sets of perpendicular undulations developed (parallel and perpendicular to the drawing axis), with wavelengths in the 100 μm range. This phenomenon, observed for the first time on bulk materials, is interpreted in terms of the Grinfeld instability: the associated wavelength, calculated in the case of a shear stress discontinuity at the interface between b.c.c. tantalum and f.c.c. copper, is found in the right magnitude range.     

Mechanical effect of process condition and abrasive concentration on material removal rate profile in copper chemical mechanical planarization

Recently, many researchers have studied the material removal mechanism of copper chemical mechanical planarization (CMP). On the basis of their previous works, we studied the mechanical effect of copper (Cu) CMP on the material removal rate profile. Copper CMP was performed using citric acid (C₆H₈O₇), hydrogen peroxide (H₂O₂), colloidal silica, and benzotriazole (BTA, C₆H₄N₃H) as a complexing agent, an oxidizer, an abrasive, and a corrosion inhibitor, respectively. In this paper, the abrasives and process condition are main mechanical factors of CMP. The colloidal silica, used as an abrasive in copper CMP slurry containing 0.01 M citric acid and 3 vol% hydrogen peroxide, controlled the wafer edge profile by abrading the wafer edge. The polishing pressure did not contribute to the material removal rate (MRR) profile, but did to the MRR. As the rotational velocity of the polishing head and table increased, the deviation of MRR profile became smaller. The results of this paper showed that the abrasive concentration was the key factor which controlled the wafer edge profile, and also the rotational velocity was the key factor which controlled wafer center profile of MRR.     

The use of solid-oxide-membrane technology for electrometallurgy

Solid oxide membrane (SOM) technology has been employed in developing several new metal reduction technologies. This overview describes the SOM process for copper deoxidation and SOM technology for metal smelting, as well as applications to magnesium, titanium, and tantalum. The examples illustrate various configurations of the SOM, anode, and cathode that are best suited to the needs of each metal.     

The evolution of diffusion barriers in copper metallization

Refractory metal nitride thin films have been widely developed as the diffusion barriers for the aluminum or copper interconnects in integrated circuits. This study reviewed the evolution of diffusion barriers in copper metallization. First, materials characteristics and electrical properties of various diffusion barriers, titanium nitride (TiN), tantalum nitride (TaN), and titanium zirconium nitride (TiZrN), were examined. These diffusion barriers were prepared by reactive magnetron sputtering in N₂/Ar gas mixtures. Next, barrier performance was evaluated by annealing the Cu/barrier/Si systems at 400–1,000°C for 60 min. in vacuum as well as the measurements of copper diffusion coefficients. The results suggest that TiZrN films can be used as a diffusion barrier for copper metallization better than the well-known TaN films. Therefore, the evolution of diffusion barriers in copper metallization, from TiN to TaN and then from TaN to TiZrN, is addressed.     

Copper diffusion into silicon substrates through TaN and Ta/TaN multilayer barriers

A study of copper (Cu) diffusion into silicon substrates through Ta nitride (TaN) and tantalum (Ta/TaN) layers was investigated based on an experimental approach. TaN _x and Ta/TaN _x thin films were deposited by radiofrequency sputtering under argon (Ar) and Ar-nitrogen (N) plasma. The influence of the N₂ partial pressure on the microstructure and the electrical properties is reported. X-ray diffraction patterns showed that the increase of the N₂ partial pressure, from 2 to 10.7%, induces a change in the composition of the δTaN phase, from TaN to TaN_1.13, as well as an evolution of the dominant crystallographic orientation. This composition change is related to a drastic increase of the electrical resistivity over a N₂ partial pressure of 7.3%. The efficiency of TaN layers and Ta/TaN multilayer diffusion barriers was investigated after annealing at temperatures between 600 and 900 °C in vacuum. Secondary ion mass spectrometry profiles showed that Cu diffuses from the surface layer through the TaN barrier from 600 °C. Cu diffusion mechanisms are modified in the presence of a Ta sublayer. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of the University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

Characteristics of the failure of tool materials

Tool materials for metal cutting tools, with hardness exceeding 62 HRC as a rule, are destroyed, in distinction to most structural steels and alloys, by brittle failure without any noticeable macroscopic deformation. The article examines the characteristics of such failure.A paper based on the present article was read at the first conference of metal scientists held at Penza, September 23–24, 1993 (discussion article)Moscow Technical State University Stankin. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 4, pp. 17–22, April, 1994.     

Combined ultrasonic vibration and chemical mechanical polishing of copper substrates

This paper introduces an ultrasonic, vibration-assisted, chemical mechanical polishing (UV-CMP) method and an ultrasonic, vibration-assisted, traditional diamond disk (UV-TDD) dressing method. A copper substrate is polished by traditional CMP and UV-CMP. UV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) with small-amplitude, high-frequency tool vibration to improve the fabrication process and machining efficiency. The removal rate of the copper substrate, torque force, and polished surface morphology of CMP and UV-CMP are compared. The polishing pad is also dressed by traditional diamond disk (TDD) and UV-TDD. The pad cut rate, torque force, and pad surface profiles of TDD and UV-TDD are also investigated in experiments. Experimental results reveal that UV-TDD can produce twice the pad cut rate and reduce torque force compared to TDD. Consequently, a dressing time reduction by half is expected, and hence, the diamond life is extended. It is found that the removal rate of the copper substrate polished by UV-CMP is increased by approximately 50-90% relative to that of traditional CMP because in UV-CMP, a passive layer on the copper surface, formed by the chemical action of the slurry, will be removed not only by the mechanical action of CMP but also by ultrasonic action. In addition, the surface roughness improves and the torque force reduces dramatically. This result suggests that the combination processes of CMP/USM and TDD/USM are feasible methods for improving polishing and dressing efficiency.     

面阵列封装互连结构热循环翘曲变形抗力

借助有限元软件对钎料球、钎料柱和铜柱阵列互连结构热循环载荷下的翘曲变形行为进行研究. 结果表明，三者升温过程均表现为刚度低的树脂基板呈下凹变形、而降温至0 ℃后呈现上凸变形，变形规律相同. 不同温度下两端基板的热膨胀系数差异引发的基板内及相连焊球/焊柱内的应力及力矩是翘曲变形发生的驱动力. 两焊柱阵列互连的基板翘曲位移接近，但均明显低于焊球阵列的基板，翘曲变形抗力更大. –40~125 ℃热循环温度范围及基板尺寸条件下，铜柱未屈服，相对钎料柱阵列互连，未表现铜柱可挠曲变形释放应力的优势.     

Multilayer coatings by chemical vapor deposition in a fluidized bed reactor at atmospheric pressure (AP/FBR-CVD): TiN/TaN and TiN/W

TiN/W and TiN/TaN multilayer coatings were deposited on stainless steel by Chemical Vapor Deposition in a Fluidized Bed Reactor at Atmospheric Pressure (AP/FBR-CVD). First, the conditions for the deposition of TiN single layers were investigated, both from the experiment and thermochemical estimations. TiN was deposited from TiCl₄ and NH₃ at temperatures in the range of 750-950 °C. In the synthesis of multilayers, the W- and Ta-based layers were obtained by reduction of tungsten chloride or tantalum chloride with H₂. During the deposition of the TiN layers on top of the Ta layers, Ta reacted with NH₃ to form a mixture of tantalum nitrides. Multilayer coatings were characterized by means of GD-OES, AES and XRD. Preliminary results of nanoindentation hardness and oxidation resistance are also presented. Our results show for the first time that AP/FBR-CVD can be tuned for the deposition of multilayered coatings with periodicities in the submicron range.     

Materials issues in area-array microelectronic packaging

The important issues in advanced area-array electronic packaging for semiconductor devices are materials driven. Some of the processing-driven materials issues include the effect of introducing a silicon device interface with copper pads and a low-κ dielectric, the effect of decreasing pitch and feature size on the package interconnects, the development and implementation of organic substrates, and advanced underfills for fine-pitch flip-chip applications. From a materials reliability aspect, important materials issues include enhanced solder interconnect reliability, α-particle-induced soft errors, and the introduction of lead-free solder alloys. Darrel R. Frear earned his Ph.D. in materials science at the University of California at Berkeley in 1987. He is currently manager of the low-cost flip-chip project at Sematech. Dr. Frear is also a member of TMS.     

芯片制程中金属互连工艺及其相关理论研究进展

随着芯片制程中互连线尺寸的不断减小,集成电路技术已经从以晶体管为中心的时代发展到以互连为中心的时代.传统的互连金属——铝、铜,在互连线性能和可靠性方面渐渐无法满足人们的需求.钴在微纳尺度下因具有更好的电性能,有可能取代铜而成为新的互连线金属,现已受到广泛关注.首先对芯片金属互连技术的历史和发展进行了综述,分别介绍了铝互连、铜互连的优点、存在的缺陷与改进方法,并对新一代钴互连技术进行了介绍,同时对潜在的互连材料,如钌、金、纳米碳材料等进行了总结.之后论述了超填充铜和超填充钴的相关机理,如铜的扩散-吸附整平机理、曲率增强加速剂覆盖机制(CEAC)以及钴的氢诱导失活机制、电压性依赖抑制机制、S型负微分电阻机制(S-NDR)、差动电流效率填充机制等.最后对铜超填充和钴超填充过程中的形核和生长过程的研究现状进行了分析,对不同镀液体系、基底材料、电镀工艺等对铜和钴的形核和生长的影响进行了归纳总结,以期对未来钴互连的研究提供帮助.     

钽等离子体渗氮的表面过程分析

对钽表面渗氮的固－气界面反应过程进行了热力学和动力学分析,从到理论预测了各种参数（压力、气体、组成、温度、电参数等）对表面过程的影响,并借助于等离子体,在较你廿获得由层与Ｎ在ＴＡ中的固溶体组成的表面硬化层,层为六方晶系的Ｔａ６Ｎ２,５７和／或非昌态。通过调整工艺参数有效地抑制了钽表面氧的渗入和Ｔａ２Ｏ５的形成,使得离子渗氮后,仍保持较低的表面粗糙度。     

Transport numbers of metal and oxygen species in anodic tantala

The transport numbers of metal and oxygen species have been determined in amorphous anodic tantala films, using transmission electron microscopy to locate ion-implanted xenon marker layers within the films. The films were formed on sputtering-deposited tantalum at constant current density, in the range 0.01-10 mA cm⁻², in 0.06 wt% H₃PO₄ solution at either 20 or 85 °C. The films grow by migration of metal and oxygen species through the film thickness, with formation of new film material at the film/electrolyte and metal/film interfaces respectively. The cation transport number, t⁺, increases due to either increase in current density or decrease in temperature: for current densities in the selected range, t⁺ increases from 0.18 to 0.32 at 20 °C, and from 0.14 to 0.29 at 85 °C. Low concentrations of phosphorus species, incorporated into an outer layer of the film, migrate inward during film growth. The migration rates are slower than those of oxygen species, by a factor in the range 0.2-0.3.     

Korrosionsbeständige chemische Apparaturen aus explosionsplattiertem Tantal

Explosion-clad sheet metal for corrosion resistant chemical equipment Explosion cladding operates without external heat input and does not require haftintermediate bonding layers. The process Prakis practically independent from the base metal. As a consequence, the tantalum layer obtained is extremely pure and of geuniform thickness. The compound material is characterized by high shear and flexural strengths. These experimental experiences have been used in designing an autoclave (120 litres) of carbon steel with Ta cladding. The design required the development of a new welding technoloy, in order to prevent Ta becoming contaminated by iron pickup. According to this method the steel is welded first, after having been reinforced by Ta inserts below the tantulum layer; this me thod facilitates the subsequent welding of the tantalum side. The welding method is used for repair purposes, too. Similar autoclaves having capacities up to 6000 litres are in the design stage.     

Korrosionsschutz durch Auftragschweißen mit den reaktiven Metallen Titan,Tantal und Zirkonium

Corrosion protection using surface-welded titanium, tantalum and zirconium claddings Very stringent demands are imposed on the corrosion resistance properties of components, apparatus, and plants of the chemical industry as well as in apparatus and machine construction. For technical and economic reasons, composite-layer materials which withstand the mechanical and corrosive conditions are employed. The special-purpose metals, titanium, tantalum, and zirconium exhibit high resistance to corrosion by many aggressive media, even at high pressure and temperature; these properties are not achieved by any of the conventional corrosion-resistant materials under the same conditions. The object of the research work was to develop a basis for producing claddings of titanium, tantalum, and zirconium by weld surfacing on a base metal of different composition with the application of the PHS method. Within the scope of the present project, single-layer claddings were applied by PHS weld surfacing with the use of titanium, tantalum, and zirconium of high purity as cladding materials on intermediate layers of nickel and copper, or alloys of these plasma hot wire weld surfacing, titanium, tantalum, zirconium, dilution, intermetallic phases, bonding, ductility elements. Boiler plate HI1 was employed as substrate for the three-layer composite materials. The titanium claddings thus applied have been thoroughly examined by metallographic techniques, layer analysis, and corrosion chemistry. The results indicate the possibility of producing corrosion-resistant claddings of titanium by the PHS method, provided that the welding process is shielded against contamination by atmospheric gases, and the formation of undesirable reaction products in the bonding zone between the base metal and filler material is minimized by means of an intermediate layer. The corrosion resistance of the surface-welded titanium claddings on an intermediate nickel layer coincides extensively with that of the reference material. On the basis of the corrosion analyses, the surface-welded titanium cladding on an intermediate copper layer is not resistant to corrosion. The results of weld surfacing with titanium have been applied to heterogeneous PHS weld surfacing with the special purpose metals tantalum and zirconium. In principle, metallographic examinations verify the possibility of producing a flawless bond between a cladding of zirconium and an intermediate nickel layer. In comparison with the filler material, Zr 702, however, the zirconium claddings applied by PHS weld surfacing exhibit a considerably greater hardness and low ductility. Because of the large difference between the melting points of tantalum and the substrate material, claddings of this kind cannot be reproducibly manufactured with sufficient quality by the PHS method, since the necessary parameters are at the extreme limit of the feasible range as far as the heat transfer is concerned.     

钇铝石榴石晶体化学机械抛光液成分优化研究

钇铝石榴石(YAG)晶体由于其优异的物理化学和光学性能,广泛用作激光器的激光增益介质。然而,目前的加工方法很难满足YAG晶体的高效高质量加工。基于传统硅溶胶抛光液的抛光机理,配制一种化学机械抛光液,并通过正交试验优化化学机械抛光液的成分配比。使用优化后的抛光液抛光YAG晶体,其化学机械抛光材料去除率提升至34 nm/min,抛光后YAG晶体表面粗糙度为0.5 nm。相比于传统硅溶胶抛光液,新型抛光液的抛光效率提升240%,抛光工件的表面粗糙度降低17%。同时,通过对比抛光液性能提出化学机械抛光界面的相互作用模式对材料去除率的影响原因。