Modification of ultra low-k dielectric films by O₂ and CO₂ plasmas

Low-k materials developed for ULSI interconnects should have sufficient resistance to processing plasma. CO2 plasma is being considered as a promising candidate for low damage photoresist ash and as a surface activation chemistry for self-assembled monolayers and atomic layer deposition on low-k materials. This article explores the interaction of two organosilicate (OSG) based low-k materials with different k-values (OSG2.4 and OSG2.2) with CO2 plasma in both CCP and ICP-remote plasma chambers. Time dependent exposure of the materials to CO2 plasma revealed quick and effective sealing of OSG2.4 surface whereas it takes longer time for OSG2.2. The sealing reduces further plasma damage and leads to accumulation of CO2 in the pores of both materials. The same behavior occurs in ICP-remote plasma but without a complete sealing of the surface. This suggests the important role of ion bombardment. Damage to low-k by conventional O-2 plasma was studied alongside and it was found that for t 60 s. Furthermore, lesser time exposure to CO2 plasma was investigated with respect to source power at constant pressure and it was discovered that damage although small, increases with varying source power

UV cure of oxycarbosilane low-k films

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Effects of methyl terminal and carbon bridging groups ratio on critical properties of porous organosilicate-glass films

Organosilicate glass-based porous low dielectic constant films with different ratios of terminal methyl to bridging organic (methylene, ethylene and 1,4-phenylene) groups are spin-on deposited by using a mixture of alkylenesiloxane with organic bridges and methyltrimethoxysilane, followed by soft baking at 120–200◦ C and curing at 430◦ C. The films’ porosity was controlled by using sacrificial template Brij® L4. Changes of the films’ refractive indices, mechanical properties, k-values, porosity and pore structure versus chemical composition of the film’s matrix are evaluated and compared with methyl-terminated low-k materials. The chemical resistance of the films to annealing in oxygen-containing atmosphere is evaluated by using density functional theory (DFT). It is found that the introduction of bridging groups changes their porosity and pore structure, increases Young’s modulus, but the improvement of mechanical properties happens simultaneously with the increase in the refractive index and k-value. The 1,4-phenylene bridging groups have the strongest impact on the films’ properties. Mechanisms of oxidative degradation of carbon bridges are studied and it is shown that 1,4-phenylene-bridged films have the highest stability. Methylene-and ethylene-bridged films are less stable but methylene-bridged films show slightly higher stability than ethylene-bridged films. © 2020 by the authors. Licensee MDPI, Basel, Switzerland

Superconductivity in a disordered metal with Coulomb interactions

We study the electronic densities of states (DOS) of strongly disordered superconducting thin films of TiN. We find, using Scanning Tunneling Microscopy (STM) that the DOS decreases towards the Fermi level in the normal phase obtained by applying magnetic fields. The DOS shows spatial fluctuations whose length scale is related to the energy dependent DOS and is similar in normal and superconducting phases. This suggests that Coulomb interactions lead to a spatially varying DOS in the normal phase of a disordered superconductor

Dual threshold diode based on the superconductor-to-insulator transition in ultrathin TiN filmss

We investigate transport properties of superconducting TiN films in the vicinity of the superconductor-insulator transition (SIT). We show that the current-voltage (I-V) characteristics are mirror-symmetric with respect to the SIT and can be switched to each other by the applied magnetic field. In both superconducting and insulating states, the low-temperature I-V characteristics have pronounced diode-like threshold character, demonstrating voltage/current jumps over several orders of magnitude at the corresponding critical current or threshold voltage. We have found that for both states, the theory developed for Josephson junction arrays offers a quantitative description of the experimental results

Influence of the ion bombardment of O₂ plasmas on low-k materials

In this study, special tests were devised in order to investigate the influence of ion bombardment on the damage induced in low-k dielectrics by oxygen plasmas. By placing a sample that suffered a lot of ion bombardment and one which suffered little ion bombardment simultaneously in the same plasma, it was possible to verify that ion bombardment in fact helped to protect the low-k film against oxygen plasma induced damage. Exhaustive analyses (ellipsometry, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, porosimetry, capacitance–voltage (C–V) measurements, water contact angle analysis) show that ion bombardment induced the formation of a denser top layer in the film, which then hampered further penetration of active oxygen species deeper into the bulk. This was further confirmed by other tests combining capacitively and inductively coupled plasmas. Therefore, it was possible to conclude that, at least for these plasmas, ion bombardment may help to reduce plasma induced damage to low-k materials

Advanced Interconnects: Materials, Processing, and Reliability

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Impact of Plasma Pretreatment and Pore Size on the Sealing of Ultra-Low-k Dielectrics by Self-Assembled Monolayers

Self-assembled monolayers (SAMs) from an 11-cyanoundecyltrichlorosilane (CN-SAM) precursor were deposited on porous SiCOH low-k dielectrics with three different pore radii, namely, 1.7, 0.7, and lower than 0.5 nm. The low-k dielectrics were first pretreated with either O2 or He/H2 plasma in order to generate silanol groups on the hydrophobic pristine surface. Subsequently, the SAMs were chemically grafted to the silanol groups on the low-k surface. The SAMs distribution in the low-k films depends on the pore diameter: if the pore diameter is smaller than the size of the SAMs precursors, the SAM molecules are confined to the surface, while if the pore diameter exceeds the van der Waals radius of the SAMs precursor, the SAMs molecules reach deeper in the dielectric. In the latter case, when the pore sidewalls are made hydrophilic by the plasma treatment, the chemical grafting of the SAM precursors follows the profile of the generated silanol groups. The modification depth induced by the O2 plasma is governed by the diffusion of the oxygen radicals into the pores, which makes it the preferred choice for microporous materials. On the other hand, the vacuum ultraviolet (VUV) light plays a critical role, which makes it more suitable for hydrolyzing mesoporous materials. In addition to the density of the surface -OH groups, the nanoscale concave curvature associated with the pores also affects the molecular packing density and ordering with respect to the self-assembly behavior on flat surfaces. A simple model which correlates the low-k pore structure with the plasma hydrophilization mechanism and the SAMs distribution in the pores is presented.status: publishe