Plasma Damage on Low-k Dielectric Materials

Low dielectric constant (low-k) materials as an interconnecting insulator in integrated circuits are essential for resistance-capacitance (RC) time delay reduction. Plasma technology is widely used for the fabrication of the interconnects, such as dielectric etching, resisting ashing or stripping, barrier metal deposition, and surface treatment. During these processes, low-k dielectric materials may be exposed to the plasma environments. The generated reactive species from the plasma react with the low-k dielectric materials. The reaction involves physical and chemical effects, causing degradations for low-k dielectric materials. This is called “plasma damage” on low-k dielectric materials. Therefore, this chapter is an attempt to provide an overview of plasma damage on the low-k dielectric materials

Design of broadband antireflective layer stacks with low surface energy prepared by sol-gel method on glass for photovoltaic application

236 p.En el Capítulo 1 de este trabajo de investigación, se introducen los aspectos relevantes relativos la tecnología fotovoltaica, tales como los tipos de células solares, así como la forma en la que estas células se integran en el módulo, y algunos requerimientos de los materiales. A continuación, se introducen los materiales, tecnologías y rutas de síntesis más prometedoras que permiten depositar recubrimientos anti-reflectantes mecánicamente robustos, con propiedades combinadas de anti-ensuciamiento. Las técnicas experimentales, sus fundamentos físicos, y el equipamiento utilizado para el desarrollo del trabajo se describen en el Capítulo 2. En el Capítulo 3, se presenta el diseño óptico teórico del sistema de recubrimientos que permiten maximizar la transmitancia óptica, en el rango de longitudes de onda en los que determinados tipos de células solares son activas. A continuación, se presenta el método experimental de síntesis de los recubrimientos cuyas cualidades objetivo has sido obtenidas en el cálculo teórico. En el Capítulo 4 se han preparado recubrimientos ó funcionalizaciones para obtener superficies con baja energía libre superficial que potencialmente repelan el agua, contaminantes y polvo. En el Capítulo 5, los sistemas de recubrimiento más prometedores se han sometido a una batería más completa ensayos de fiabilidad, algunos de ellos utilizados por la industria fotovoltaica para validar los materiales y componentes utilizados en la fabricación de módulos fotovoltaicos. Este trabajo de investigación se concluye con un Capitulo 6 que contiene conclusiones generales, líneas futuras y producción científica

Interaction between plasma and low-k dielectric materials

textWith the scaling of devices, integration of porous ultra low-κ dielectric materials into Cu interconnect becomes necessary. Low-k dielectric materials usually consist of a certain number of methyl groups and pores incorporated into a SiO₂ backbone structure to reduce the dielectric constant. They are frequently exposed to various plasmas, since plasma is widely used in VLSI semiconductor fabrication such as etching, ashing and deposition. This dissertation is aimed at exploring the interaction between plasma and low-κ dielectric surfaces. First, plasma assisted the atomic layer deposition (ALD) of Ta-based Cu barriers. Atomic layer deposition of Ta barriers is a self-limited surface reaction, determined by the function groups on the low-κ dielectric surface. But it was found TaCl₅ precursor could not nucleate on the organosilicate low-κ surface that was terminated with methyl groups. Radical NH[subscript x] beam, generated by a microwave plasma source, could activate the surface through exchanging with the methyl groups on the low-κ surface and providing active Si-NH[subscript x] nucleation sites for TaCl₅ precursors. Results from Monte Carlo simulation of the atomic layer deposition demonstrated that substrate chemistry was critical in controlling the film morphology. Second, the properties of low-κ dielectric materials tended to degrade under plasma exposure. In this dissertation, plasma damage of low-κ dielectric surface was investigated from a mechanistic point of view. Both carbon depletion and surface densification were observed on the top surface of damaged low-κ materials while the bulk remained largely uninfluenced. Plasma damage was found to be a complicated phenomenon involving both chemical and physical effects, depending on chemical reactivity and the energy and mass of the plasma species. With a downstream plasma source capable of separating ions from the plasma beam and an in-situ x-ray photoelectron spectroscopy (XPS) monitoring of the damage process, it was clear that ions played a more important role in the plasma damage process. Increase of dielectric constant after plasma damage was mainly attributed to moisture uptake and was confirmed with quantum chemistry calculation. Annealing was found to be effective in mitigating moisture uptake and thus restoring κ value. Finally, oxygen plasma damage to blanket and patterned low-κ dielectrics was studied in detail. Energetic ions in oxygen plasma contributed much to the loss of film hydrophobicity and dielectric constant through the formation of C=O and Si-OH. Based on results from residual gas analyses (RGA), three possible reaction paths leading to carbon depletion were proposed. This was followed by analytical solution of the evolution of carbon concentration during O₂ plasma damage. O₂ plasma damage to patterned CDO film was studied by TEM/EELS. And the damage behavior was simulated with Monte Carlo method. It was found that the charging potential distribution induced by plasma was important in determining the carbon loss in patterned low-k films. The charging potential distribution was mainly related to the geometry of low-k trench structures. To recover the dielectric constant, several recovery techniques were tried and briefly discussed.Physic

Design of broadband antireflective layer stacks with low surface energy prepared by sol-gel method on glass for photovoltaic application

236 p.En el Capítulo 1 de este trabajo de investigación, se introducen los aspectos relevantes relativos la tecnología fotovoltaica, tales como los tipos de células solares, así como la forma en la que estas células se integran en el módulo, y algunos requerimientos de los materiales. A continuación, se introducen los materiales, tecnologías y rutas de síntesis más prometedoras que permiten depositar recubrimientos anti-reflectantes mecánicamente robustos, con propiedades combinadas de anti-ensuciamiento. Las técnicas experimentales, sus fundamentos físicos, y el equipamiento utilizado para el desarrollo del trabajo se describen en el Capítulo 2. En el Capítulo 3, se presenta el diseño óptico teórico del sistema de recubrimientos que permiten maximizar la transmitancia óptica, en el rango de longitudes de onda en los que determinados tipos de células solares son activas. A continuación, se presenta el método experimental de síntesis de los recubrimientos cuyas cualidades objetivo has sido obtenidas en el cálculo teórico. En el Capítulo 4 se han preparado recubrimientos ó funcionalizaciones para obtener superficies con baja energía libre superficial que potencialmente repelan el agua, contaminantes y polvo. En el Capítulo 5, los sistemas de recubrimiento más prometedores se han sometido a una batería más completa ensayos de fiabilidad, algunos de ellos utilizados por la industria fotovoltaica para validar los materiales y componentes utilizados en la fabricación de módulos fotovoltaicos. Este trabajo de investigación se concluye con un Capitulo 6 que contiene conclusiones generales, líneas futuras y producción científica

Copper Metal for Semiconductor Interconnects

Resistance-capacitance (RC) delay produced by the interconnects limits the speed of the integrated circuits from 0.25 mm technology node. Copper (Cu) had been used to replace aluminum (Al) as an interconnecting conductor in order to reduce the resistance. In this chapter, the deposition method of Cu films and the interconnect fabrication with Cu metallization are introduced. The resulting integration and reliability challenges are addressed as well

Developing Metrology for Nondestructive Characterization of Buried Polymer Interfaces in Situ.

Polymers are widely used in modern microelectronics as adhesives, organic substrates, chip passivation layers, insulating dielectric materials, and photoresists in microlithography. The interfacial structures of polymer materials determine the interfacial properties of the materials. Weak adhesion or delamination at interfaces involving polymer materials can lead to failure of microelectronic devices. Therefore, it is important to investigate the molecular structures of such interfaces. However, it is difficult to study molecular structures of buried interfaces due to a lack of appropriate analytical techniques. This dissertation presents the development of the nonlinear optical technique sum frequency generation (SFG) vibrational spectroscopy into a metrology tool for nondestructive characterization of molecular structures at buried polymer interfaces in microelectronic packages in situ and the elucidation of relationships between buried molecular structures and interfacial properties such as adhesion strength. Buried polymer/epoxy, copper/epoxy, and silicon/organosilicate dielectric interfaces were investigated. SFG was used to directly probe molecular structures at buried adhesive interface in situ. Plasma treatment of polymer surfaces was found to alter the molecular structure at corresponding buried interfaces prepared using the plasma treated surfaces. Hygrothermal aging treatment was found to influence hydrophobic polymer/polymer interfaces less than hydrophilic interfaces, showing that hydrophobic materials can better resist delamination during qualification testing in high humidity environments. Copper/epoxy interfaces were found to delaminate near, but not exactly at, the metal/polymer interface and silane adhesion promoters were found to modify the interfacial region near the copper surface which suggests that the interfacial layer near copper needs to be modified to improve adhesion. Quantitative data analysis methodology was developed to simultaneously characterize the surface and buried interface of silicon-supported thin low-k polymer films nondestructively before and after microelectronic processing steps which provided a molecular level understanding of the effects of the processing. The general nature of the methodology enables it to be directly utilized to elucidate structure-property relationships at buried interfaces by correlating interfacial structures to interfacial properties. Structure-property relationships elucidated using this methodology can be used to guide the rational engineering of buried polymer interfaces with optimized properties in many practical applications such as polymer composites, optical fibers, paints, and anticorrosion coatings.PhDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/133179/1/myersjn_1.pd