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

In Situ IR Spectroscopic Investigation of Alumina ALD on Porous Silica Films: Thermal versus Plasma-Enhanced ALD

A novel in situ infrared (IR) approach is demonstrated for investigating and identifying ALD surface reactions during both the steady state and the initial growth regime. The unique combination of reflection−absorption IR spectroscopy in grazing incidence mode with a high surface area reflecting substrate allows for ALD process monitoring with an acceptable acquisition time and a high sensitivity in the entire mid-IR spectral region. Using a mesoporous silica film deposited on a reflecting platinum layer as substrate, the thermal and plasma-enhanced ALD processes of alumina with use of trimethylaluminum (TMA) are compared. Due to the high sensitivity of the method, the relative amount of surface hydroxyl groups added or removed during the process could be determined versus the number of ALD half-cycles. These data reveal substrate-inhibited growth on the silica surface for the thermal process with use of TMA and water, as compared to direct growth for the plasma-based ALD process with use of TMA and O2 plasma. This different behavior could be linked to the formation of Si−CH3 surface groups after the first precursor pulse, as evidenced by the raw IR spectra. It is found that the oxygen radicals in the plasma can remove these surface groups during the next few ALD cycles, while the H2O molecules cannot, thus explaining the initial slower growth for the thermal process.status: publishe

Study of the surface species during thermal and plasma-enhanced atomic layer deposition of titanium oxide films using in situ IR-spectroscopy and in vacuo X-ray photoelectron spectroscopy

The thermal and plasma-enhanced atomic layer deposition (ALD) growth of titanium oxide using an alkylamine precursor - tetrakis(dimethylamino)titanium (TDMAT) - was investigated. The surface species present during both the precursor and co-reactant pulse were studied with in situ reflection mid-IR spectroscopy (FTIR) and in vacuo X-ray photoelectron spectroscopy (XPS). The thermal process using H2O vapor proceeds through a typical ligand exchange reaction mechanism. The plasma-enhanced ALD processes using H2O-plasma or O-2-plasma exhibit an additional decomposition and combustion reaction mechanism. After the plasma exposure, imine (N & xe001;C) and isocyanate (N & xe001;C & xe001;O) surface species were observed by in situ FTIR. In addition, nitrites (NOx) were detected using in vacuo XPS during the O-2-plasma process. This study presents the importance of the use of in situ FTIR and in vacuo XPS as complementary techniques to learn more about the ALD reaction mechanism. While in situ FTIR is very sensitive to changes of chemical bonds at the surface, exact identification and quantification could only be done with the aid of in vacuo XPS

Atomic layer deposition of TiO₂ on surface modified nanoporous low-k films

This paper explores the effects of different plasma treatments on low dielectric constant (low-k) materials and the consequences for the growth behavior of atomic layer deposition (ALD) on these modified substrates. An O2 and a He/H2 plasma treatment were performed on SiCOH low-k films to modify their chemical surface groups. Transmission FTIR and water contact angle (WCA) analysis showed that the O2 plasma changed the hydrophobic surface completely into a hydrophilic surface, while the He/H2 plasma changed it only partially. In a next step, in situ X-ray fluorescence (XRF), ellipsometric porosimetry (EP), and Rutherford backscattering spectroscopy (RBS) were used to characterize ALD growth of TiO2 on these substrates. The initial growth of TiO2 was found to be inhibited in the original low-k film containing only Si-CH3 surface groups, while immediate growth was observed in the hydrophilic O2 plasma treated film. The latter film was uniformly filled with TiO2 after 8 ALD cycles, while pore filling was delayed to 17 ALD cycles in the hydrophobic film. For the He/H2 plasma treated film, containing both Si-OH and Si-CH3 groups, the in situ XRF data showed that TiO2 could no longer be deposited in the He/H2 plasma treated film after 8 ALD cycles, while EP measurements revealed a remaining porosity. This can be explained by the faster deposition of TiO2 in the hydrophilic top part of the film than in the hydrophobic bulk which leaves the bulk porous, as confirmed by RBS depth profiling. The outcome of this research is not only of interest for the development of advanced interconnects in ULSI technology, but also demonstrates that ALD combined with RBS analysis is a handy approach to analyze the modifications induced by a plasma treatment on a nanoporous thin film

Pore Narrowing of Mesoporous Silica Materials

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