Academic literature on the topic 'Low-k dielectric materials'

Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity toward aluminum chemical vapor deposition. Silicon-carbon (Si-Cx) films were formed by electron beam bombardment of trimethylvinylsilane films which were adsorbed onto metal substrates at low temperatures in ultra-high vacuum. Oxygen was also added to the films by coadsorbing water before electron beam bombardment; the films were stable to more than 700 K, with increasing silicon-oxygen bond formation at elevated temperatures. Copper metal was sputter deposited in small increments onto non-oxygenated films. X-ray photoelectric spectra show three-dimensional copper growth (rather than layer-by-layer growth), indicating only weak interaction between the copper and underlying films. Annealing at elevated temperatures caused coalescence or growth of the copper islands, with spectra indicating metallic copper rather than copper oxide.

<p> Low-k dielectrics have been incorporated into advanced computer chip technologies as a part of the continuous effort to improve computer chip performance. One drawback associated with the implementation of low-k dielectrics is the large leakage current which conducts through the material, relative to silica. Another drawback is that the breakdown voltage of low-k dielectrics is low, relative to silica [1]. This low breakdown voltage makes accurate reliability assessment of the failure mode time dependent dielectric breakdown (TDDB) in low-k dielectrics critical for the successful implementation of these materials. The accuracy with which one can assess this reliability is currently a topic of debate. </p><p> These material drawbacks have motivated the present work which aims both to contribute to the understanding of electronic conduction mechanisms in low-k dielectrics, and to improve the ability to experimentally characterize changes which occur within the material prior to TDDB failure. What follows is a study of the influence of an applied magnetic field on the conductivity of a low-k dielectric, or in other words, a study of the material&rsquo;s magnetoresistance. </p><p> This study shows that low-k dielectrics used as intra-level dielectrics exhibit a relatively large negative magnetoresistance effect (&sim;2%) at room temperature and with modest applied magnetic fields (&sim;100 Oe). The magnetoresistance is attributed to the spin dependence of trapping electrons from the conduction band into localized electronic sites. Mixing of two-electron spin states via interactions between electron spins and the the spins of hydrogen nuclei is suppressed by an applied magnetic field. As a result, the rate of trapping is reduced, and the conductivity of the material increases. </p><p> This study further demonstrates that the magnitude of the magnetoresistance changes as a function of time subjected to electrical bias and temperature stress. The rate that the magnetoresistance changes correlates to the intensity with which the material was stressed. It is postulated that the change in magnetoresistance which occurs as a result of bias temperature stress could be used as an alias for measuring the degradation which contributes to TDDB. </p><p> Finally, it is shown that the magnetoresistance behavior is non-monotonic. That is, for small values of applied magnetic field (&sim;2 Oe) the conductivity initially decreases, while for further increase of the magnetic field the conductivity increases to a saturation. The non-monotonic behavior is consistently described in the context of competing spin mixing mechanisms.</p>

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1999.<br>Includes bibliographical references (leaves 108-111).<br>Junction capacitance measurement is a well-established powerful characterization technique that allows one to explore electrical and physical properties of defects in bulk and interface of electronic materials. Capacitance-Voltage (CV) measures the overall net carrier concentration and a built-in voltage for a diode junction. Deep level transient spectroscopy (DLTS) as one of the most sensitive electrical measurement techniques can detect electrically active impurity concentration on the level of 10-1 to 10-5 of substrate doping concentration. The characteristic energy level and capture cross-section of the traps in the semiconductor energy gap can be extracted from DLTS temperature scans. Coupled with CV free carrier concentration profile, isothermal profiling by DLTS can determine the distribution of electrically active defects in the semiconductor. CV can also measure dielectric constant, K, on a metal-oxide-silicon structure. In this thesis, the junction capacitance technique is a primary tool used to study Er, Fe, and Mo in silicon. Si:5r is a candidate system for a light emitter in Si-based microphotonics. Fe is one of the most troublesome elements that degrade integrated circuit performance and solar cell efficiency. Mo is a fairly unknown contaminant typical of integrated circuit processing. Fluorosilicate glass is being used as a dielectric material for inter-metal levels in the current generation microprocessor. By measuring the reaction kinetics of the Er-related donor state, a defect structure for Si:Er light emitter center was deduced. The role of heterogeneous precipitation in Fe internal gettering was observed and modeled by measurement of residual [FeB] associates following [Fe] saturation, quench, and annealing processing. The diffusivity of Mo was determined and models for both the substitutional and the kick out diffusion mechanism were constructed. Finally, a predictive model for the F-content dependent dielectric constant variation of Si02 was established.<br>by Sang Hoon Ahn.<br>Ph.D.

The shift to the Cu/low-k interconnect scheme requires the development of diffusion barrier/adhesion promoter materials that provide excellent performance in preventing the diffusion and intermixing of Cu into the adjacent dielectrics. The integration of Cu with low-k materials may decrease RC delays in signal propagation but pose additional problems because such materials are often porous and contain significant amounts of carbon. Therefore barrier metal diffusion into the dielectric and the formation of interfacial carbides and oxides are of significant concern. The objective of the present research is to investigate the fundamental surface interactions between diffusion barriers and various low-k dielectric materials. Two major diffusion barriers¾ tatalum (Ta) and titanium nitride (TiN) are prepared by DC magnetron sputtering and metal-organic chemical vapor deposition (MOCVD), respectively. Surface analytical techniques, such as X-ray photoelectronic spectroscopy (XPS), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are employed. Ta sputter-deposited onto a Si-O-C low dielectric constant substrate forms a reaction layer composed of Ta oxide and TaC. The composition of the reaction layer varies with deposition rate (1 Å-min-1 vs. 2 Å-sec-1), but in both cases, the thickness of the TaC layer is found to be at least 30 Å on the basis of XPS spectra, which is corroborated with cross-sectional TEM data. Sputter-deposited Cu will not wet the TaC layer and displays facile agglomeration, even at 400 K. Deposition for longer time at 2 Å-sec-1 results in formation of a metallic Ta layer. Sputter deposited Cu wets (grows conformally) on the metallic Ta surface at 300 K, and resists significant agglomeration at up to ~ 600 K. Cu diffusion into the substrate is not observed up to 800 K in the UHV environment. Tetrakis(diethylamido) titanium (TDEAT) interactions with SiO2, Cu and a variety of low-k samples in the presence (~ 10-7 Torr or co-adsorbed) and absence of NH3 result in different products. TDEAT interactions with SiO2 are dominated by Ti interactions with substrate oxygen sites, and that Ti oxide/sub-oxide bond formation can proceed with relatively low activation energy. No Ti carbide or Si carbide formation is observed. Co-adsorption of TDEAT and NH3 on SiO2 at 120K followed by annealing to higher temperature results in enhanced Ti-N bond formation, which is stable against oxidation up to 900K in UHV. Similarly, continuous exposures of TDEAT on SiO2 at 500K in the presence of NH3 exhibit a relatively enhanced Ti-N spectral component. Co-adsorption of NH3 and TDEAT on Cu (poly) surface at 120K, followed by annealing to 500K, results in complete desorption of Ti, N or C-containing species from the Cu substrate. Reaction of TDEAT with a Cu surface at 500K yields a Ti-alkyl species via a b-hydride elimination pathway. TDEAT/Cu interactions are not observably affected by overpressures of NH3 of 10-7 Torr. TDEAT interaction with a porous carbon doped oxide low-k substrate at 700K demonstrates undissociated or partly dissociated Ti-NR species trapped in the dielectrics matrix due to its high porosity. In addition, carbide formation is observed from C(1s) XPS spectra. For a hydrocarbon low-k film, the majority sites (carbon) are highly unreactive towards TDEAT even at higher temperature due to a lack of functional groups to initiate the TDEAT/low-k surface chemistry.

A modified CVD reactor was designed with a deposition chamber capable of accomodating 8" wafers, with the capacity to remotely pyrolyze two different precursors. The design was based on a previous working reactor, with the most notable improvements being a showerhead design for more even delivery of gaseous precursor and a separate heating control of the substrate holder and deposition chamber walls. The performance of the reactor was analyzed by testing the pressure gradients within and the thickness uniformity of films deposited on 8" wafers. The reactor exhibited a linear pressure gradient within, and the thickness uniformity was excellent, with a slight increase in thickness towards inlet of the showerhead. The thickness difference between the maximum and minimum thickness on an 8" wafer was 14%. Films of polyparaxylylene (PPXN), polychloroparaxylylene (PPXC), SiO₂, and PPXC/SiO₂ were deposited, with deposition rates and indices of refraction comparable to those obtained on the old reactor design. A full factorial study was performed to determine the effect of the substrate temperature, the sublimation temperature, and the pyrolysis temperature on the deposition rates of PPXC. It was determined that the substrate temperature has the greatest effect, with about 50% contribution, and deposition rates increased with decreasing substrate temperature. The sublimation temperature contributed 25%, with increasing sublimation rates leading to higher deposition rates. The pyrolysis contributes very little, with about 2%, and the variance ratio did not fall within a 90% confidence level. <p> A low dielectric constant polymer, poly(tetrafluoro-p-xylylene) (VT-4), was synthesized by chemical vapor deposition from 4,5,7,8,12,13,15,16-octafluoro-[2.2]-paracyclophane (DVT-4). The main motivation was to find a cheaper alternative to poly( alpha, alpha , alpha ', alpha '-tetrafluoro-p-xylylene) (AF-4) with similar properties. The dielectric constant of VT-4 was measured as 2.42 at 1 MHz, and the in-plane and out-of-plane indices of refraction were 1.61 and 1.47 at 630 nm. The large negative birefringence suggests a low out-of-plane dielectric constant, which is desired for interlayer dielectrics. The VT-4 polymer was found to be stable at 460 ^oC by thermogravimetric analysis (TGA). <p> Polymer/Siloxane nanocomposites were studied as an alternate path to a polymer/silica composite. This study showed that incorporation of a four-ringed liquid siloxane precursor into the parylene PPXC is not feasible. A solid precursor cube-like molecule, vinyl-T8, was incorporated with ease. Pyrolysis of vinyl-T8 at different temperatures revealed complex behavior, with the formation of polymerized vinyl-T8 (through free radical addition at the vinyl groups) as well as silica-like structures forming above 500 oC as a result of the breaking up of the cage structure of vinyl-T8. Codepositions of PPXC and vinyl-T8 were then examined as a possible path towards a polymer/silica nanocomposite. At deposition temperatures below 5^o C, precipitation of excess vinyl-T8 into cubic micron-sized crystals occurred. As this was undesirable, studies were continued at higher deposition temperatures. A Taguchi orthogonal array was set up to study the effect of the sublimation temperatures of the two precursors as well as the pyrolysis temperature and the substrate temperature on the deposition rate, the index of refraction and the weight loss after a 500 ^oC anneal. The deposition rate depended mostly on the sublimation temperature of the PPXC and the substrate temperature. The lowest index of refraction (and thus the lowest dielectric constant) was obtained with the lowest sublimation temperatures of 134 ^oC for PPXC and 195^o C for vinyl-T8 and a pyrolysis temperature of 200 ^oC. Each of the factors was found to have an effect on the index of refraction, with the sublimation temperature of vinyl-T8 having the most influence. The films degraded at 500 ^oC, indicating that post-deposition annealing of the films did not lead to a conversion of the vinyl-T8 to a SiO₂ -like structure (which would be stable at that temperature). X-ray diffraction spectra of the films revealed peaks which were not present for any of the vinyl-T8 films or characteristic of PPXC. Therefore, some type of interaction between the two components occurred and affected the morphology, most likely the formation of a block copolymer. Thus, though polymer/silica films were not attained, the resulting composites had comparable properties with higher deposition rates and a cleaner process.<br>Master of Science

An alternative indirect integration regime of porous low-k materials was investigated. Based on a single Damascene structure the intra level dielectric SiO2 or damaged ULK was removed by using HF:H2O solutions to create free standing metal lines. The free spaces between the metal lines were refilled with a spin-on process of a low-k material. The persistence of barrier materials and copper against HF solutions, the gap fill behavior of the used spin on glass on different structure sizes and the main challenges which have to solve in the future are shown in this study.

In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of carbon abstraction observed for OSG exposed to O2 plasma is definitively attributed to the diffusion of O2 down OSG nanopores, reacting at photo-activated sites, rather than to the diffusion of atomic O. Pretreatment of OSG by 900 eV Ar+ ion bombardment also results in formation of 1 nm thick SiO2-like surface overlayer that inhibits O2 diffusion, inhibiting VUV+O2 and O2 plasma-induced reactions, and that the effectiveness of this treatment increases with ion kinetic energy. On the contrary, organosilicate glass (OSG) films with backbone carbon (-Si-R-Si-) exhibit significantly enhanced resistance to carbon loss upon exposure to O2 plasma, radicals and VUV+O2 compared to films with terminal methyl groups (Si-CH3). Films incorporating backbone carbon chains (-Si-R-Si-) were deposited from 1,2 bis (triethoxysilyl) ethane (BTESE) precursor by ebeam or plasma cross-linking. The radical effects on BTESE film indicates negligible carbon loss or Si oxidation, combined with C-O bond formation, under conditions where OSG films with terminal methyl groups exhibit > 80% carbon loss within the surface region of the film. C-O bond formation is never observed for terminal CH3 groups. Further, backbone carbon (-Si-R-Si-) films exposed to VUV+O2 exhibit self-limiting, minimal net carbon loss. This indicates that plasma-induced Si-C bond rupture still occurs in the linking unit, but with a low probability of simultaneous rupture of both Si-C bonds required for abstraction of an in-line methylene bridging group. The data thus demonstrate that OSG films containing backbone carbon groups exhibit greatly reduced rates of carbon loss in the presence of O2 plasma, radicals or VUV+O2 compared to films with terminal carbon groups due to fundamentally different patterns of Si-C bond scission. The results demonstrate the potential of backbone carbon low-k films to resist plasma induced damage.