Els Van Besien

Electronic structure and spectrum of UO22+ and UO2Cl42−

A theoretical study is presented of the electronic spectra of the UO(2) (2+) and UO(2)Cl(4) (2-) ions, based on multiconfigurational perturbation theory (CASSCF/CASPT2), combined with a recently developed method to treat spin-orbit coupling [P.-A. Malmqvist et al., Chem. Phys. Lett. 357, 230 (2002); B. O. Roos and P.-A. Malmqvist, Phys. Chem. Chem. Phys. 6, 2919 (2004)]. The results are compared to the experimental spectroscopic data obtained for uranyl ions in Cs(2)UO(2)Cl(4) crystals from Denning [Struct. Bonding (Berlin) 79, 215 (1992)] and to previous theoretical calculations performed using a combined configuration-interaction spin-orbit treatment [Z. Zhang and R. M. Pitzer, J. Phys. Chem. A 103, 6880 (1999); S. Matsika and R. M. Pitzer, J. Phys. Chem. A. 105, 637 (2001)]. As opposed to the latter results, the calculations performed in this work point to a significant effect of the weakly bound equatorial chlorine ligands on the excitation energies.

Electronic spectrum of UO2(2+) and [UO2Cl4]2- calculated with time-dependent density functional theory

The electronic spectra of UO(2) (2+) and [UO(2)Cl(4)](2-) are calculated with a recently proposed relativistic time-dependent density functional theory method based on the two-component zeroth-order regular approximation for the inclusion of spin-orbit coupling and a noncollinear exchange-correlation functional. All excitations out of the bonding sigma(u) (+) orbital into the nonbonding delta(u) or phi(u) orbitals for UO(2) (2+) and the corresponding excitations for [UO(2)Cl(4)](2-) are considered. Scalar relativistic vertical excitation energies are compared to values from previous calculations with the CASPT2 method. Two-component adiabatic excitation energies, U-O equilibrium distances, and symmetric stretching frequencies are compared to CASPT2 and combined configuration-interaction and spin-orbit coupling results, as well as to experimental data. The composition of the excited states in terms of the spin-orbit free states is analyzed. The results point to a significant effect of the chlorine ligands on the electronic spectrum, thereby confirming the CASPT2 results: The excitation energies are shifted and a different luminescent state is found.

Effect of UV wavelength on the hardening process of porogen-containing and porogen-free ultralow-k plasma-enhanced chemical vapor deposition dielectricsa)

The effect of narrow-band 172 nm and broad-band >200 nm UV sources in the new curing scheme of the plasma-enhanced chemical vapor deposition (PECVD) dielectrics is studied. The new curing scheme is based on porogen removal (organic sacrificial phase introduced to generate open porosity) from PECVD dielectric before its final UV curing. The results are compared with the PECVD films fabricated in the conventional scheme in which porogen is still present during the UV curing. The same curing time of porogen-containing conventional PECVD films with 172 nm and >200 nm UV sources results in only 10% difference in their Young’s modulus (YM): 5.84 and 5.32 GPa, respectively. However, the porogen-free films cured with 172 nm UV source show a YM of 6.64 GPa (k100 kHz∼2.2, 44% open porosity), approximately twice as large as those cured with >200 nm UV having a YM of 3.38 GPa (k100 kHz∼2.0, 48% open porosity). The mechanical properties, optical properties in the range of 150–800 nm, dielectric constants at 100 kHz an...

Electronic spectra of uranyl chloride complexes in acetone: a CASSCF/CASPT2 investigation

A theoretical study is presented of the electronic spectra of the complexes UO(2)Cl(2)ac(4), UO(2)Cl(2)ac(3), [UO(2)Cl(3)ac(2)](-) and [UO(2)Cl(3)ac](-) (ac = acetone) using perturbation theory based on a complete-active-space type wavefunction (CASSCF/CASPT2). Both scalar relativistic effects and spin-orbit coupling were included in the calculations. The calculated excitation energies and oscillator strength values have been compared to the experimental absorption spectrum for uranyl chloride complexes in acetone solution, for chloride-to-uranyl ratios between two and three. The main purpose of this work was to investigate the origin of the remarkable intensity increase observed in the lower part of the experimental absorption spectra, upon addition of chloride to uranyl complexes in acetone. The calculated excitation energies for the different complexes are similar and closely correspond to the experimental data. However, in none of the theoretical spectra, the high intensities observed in the lower part of the experimental spectrum are reproduced.

Integration of 20nm half pitch single damascene copper trenches by spacer-defined double patterning (SDDP) on metal hard mask (MHM)

Spacer defined double patterning (SDDP) enables further pitch scaling using 193nm immersion lithography. This work aims to design and generate 20nm half pitch (HP) back-end-of-line test structures for single damascene metallization using SDDP with a 3-mask flow. We demonstrated patterning and metallization of 20nm HP trenches in silicon oxide with TiN metal hard mask (MHM).

Hydrogen outgassing induced liner/barrier reliability degradation in through silicon via's

Degraded liner/barrier integrity is observed in 3D Cu through silicon via systems using a sub-atmospheric chemical vapor deposition O3/tetraethyl orthosilicate (TEOS) oxide liner and a physical vapor deposition Ta barrier. By analyzing the data of thermal desorption spectroscopy and Fourier transform infrared spectroscopy, the source of the degradation is found to be outgassed hydrogen from the liner. To overcome this hydrogen induced degradation, three alternative liner/barrier schemes are proposed and validated: 1) a capped O3/TEOS liner, 2) a metal barrier that is resistant to hydrogen, and 3) a denser oxide liner.

Influence of the UV Cure on Advanced Plasma Enhanced Chemical Vapour Deposition Low-

In a recent study, low-k thin films with low dielectric constant (≤2.1) and high Youngs modulus (>5 GPa) were obtained by introducing a remote plasma step between the traditional plasma enhanced chemical vapour deposition and UV curing. This study shows that the UV curing step with a narrow band lamp with wavelength of 172 nm induced more network Si–O and Si–H bonds and more densification than the curing step with a broadband lamp with wavelengths higher than 200 nm. As a consequence, the dielectric constant of the narrow band cured film was slightly higher, but Youngs modulus and hardness were much improved. Electrical characterization showed good breakdown voltages and a more than sufficient time dependent dielectric breakdown reliability. The broadband lamp was then used to form thicker films which retained very well the characteristics of the thin films.

k

Scaling of the Cu interconnect structures requires Cu capping layers with an increasingly lower dielectric constant (K) that still have adequate Cu and moisture barrier properties. In this work, we study the plasma enhanced chemical vapour (PE-CVD) deposition of amorphous silicon carbide films using dimethyl silacyclopentane (DMSCP) as a precursor, resulting in the incorporation of Si-(CH2)n-Si bridges. The effect of process parameters on film characteristics like K, mass density (p), and leakage behaviour is investigated, as well as their relation with the chemical bonding structure. Finally, Cu barrier properties and hermeticity are evaluated.

Materials

A Through Silicon Via (TSV) is a key component for 3D integrated circuit stacking technology, and the diameter of a TSV keeps scaling down to reduce the footprint in silicon. The TSV aspect ratio, defined as the TSV depth/diameter, tends to increase consequently. Starting from the aspect ratio of 10, to improve the TSV sidewall coverage and reduce the process thermal budget, the TSV dielectric liner deposition process has evolved from sub-atmospheric chemical vapour deposition to plasma-enhanced atomic layer deposition (PE-ALD). However, with this change, a strong negative shift in the flatband voltage is observed in the capacitance-voltage characteristic of the vertical metal-oxide-semiconductor (MOS) parasitic capacitor formed between the TSV copper metal and the p-Si substrate. And, no shift is present in planar MOS capacitors manufactured with the same PE-ALD oxide. By comparing the integration process of these two MOS capacitor structures, and by using Elastic Recoil Detection to study the elemental composition of our films, it is found that the origin of the negative flatband voltage shift is the positive charge trapping at the Si/SiO2 interface, due to the positive PE-ALD reactants confined to the narrow cavity of high aspect ratio TSVs. This interface charge trapping effect can be effectively mitigated by high temperature annealing. However, this is limited in the real process due to the high thermal budget. Further investigation on liner oxide process optimization is needed.A Through Silicon Via (TSV) is a key component for 3D integrated circuit stacking technology, and the diameter of a TSV keeps scaling down to reduce the footprint in silicon. The TSV aspect ratio, defined as the TSV depth/diameter, tends to increase consequently. Starting from the aspect ratio of 10, to improve the TSV sidewall coverage and reduce the process thermal budget, the TSV dielectric liner deposition process has evolved from sub-atmospheric chemical vapour deposition to plasma-enhanced atomic layer deposition (PE-ALD). However, with this change, a strong negative shift in the flatband voltage is observed in the capacitance-voltage characteristic of the vertical metal-oxide-semiconductor (MOS) parasitic capacitor formed between the TSV copper metal and the p-Si substrate. And, no shift is present in planar MOS capacitors manufactured with the same PE-ALD oxide. By comparing the integration process of these two MOS capacitor structures, and by using Elastic Recoil Detection to study the elemental ...