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Critical dimension (CD) shrink and patterning of contact features via plasma etching were studied for typical resistive random access memory (RRAM) stacks. These consist of SiO2 and Si3N4 (total thickness of 65 80 nm) with NiO or pure Ni at the bottom. First, the contact patterning of RRAM stacks was investigated for 90 nm contacts. Thus, a standard high power contact etch recipe was shown to give rise to resist strip challenges due to the incorporation of sputtered Ni in the resist film. Therefore, a low-sputter-yield contact etch recipe based on a CF4/H2/Ar gas chemistry was introduced. The ion sputter efficiency of the recipe was estimated from a blanket SiO2 sputter-yield experiment in Ar plasma for the same recipe settings: this yielded values close to the Ni sputter-yield threshold. Second, plasma-assisted CD shrink was studied in combination with the newly developed patterning scheme to get the contact CD well below the initial 90-nm litho print size. It was shown that a low contact etch power regime could also provide a larger window for contact CD shrink using a C2H4-based chemistry: e.g. the demonstrated CD shrink from 90 nm down to sub-40 nm was shown to be extremely challenging in the case of a high power regime due to polymer instability enhanced with the resulting thickness increase. Perhaps, the relaxation of the polymer film stress, which was measured to be in the range of 1200-1500 MPa, is more easily triggered at higher power settings, which leads to polymer blistering. Finally, the optimization of the plasma-assisted CD shrink step in combination with the low-sputter-yield contact etch recipe was demonstrated to be able to provide CDs as small as 27 nm. The demonstrated approach shows that plasma-assisted CD shrink can provide a robust test vehicle for research programs that require the patterning of small features in the sub-40-nm CD range.
The results of recent investigations show that after UV curing of CVD SiCOH low-k films deposited with organic material (porogen) some amount of the porogen remains in the cured films in the form of non-volatile graphitized phase, known as “porogen residue”. These residues could influence leakage current and reliability. The goal of the present work is investigation of the different parameters of UV curing that can influence amount of the porogen residue. In this work we focused generally on the study of the amount of porogen residues as function of the wavelength of curing light and the porosity of the material (amount of deposited porogen). To study the curing dependence on the wavelength, we compared optical properties (measured by spectroscopic ellipsometry) and IR adsorption (measured by FTIR) of samples cured by 172 nm monochromatic light (lamp A) with samples cured by broadband source with wavelength more than 200 nm (lamp B). To understand how the amount of porogen residue depends on the amount of deposited porogen (porosity), three films with different k-value were deposited: a film with k = 3 deposited without porogen and two porogen-based low-k with target k-value of 2.5 and 2.3. Furthermore, taking into account that He/H2 plasma effectively removes the porogen residues from porous films without any plasma damage of the matrix material, we exposed the films to that plasma. Then these films were cured by broadband lamp at different temperatures and amount of porogen residues was measured by ellipsometry. It was found that He/H2 plasma cannot fully remove the porogen and causes film shrinkage. The Subsequent UV curing does not produce significant changes.
As conventional materials in CMOS manufacturing, Si as a gate material and SiO2 as a gate dielectric, approach their performance limit, the search for new materials becomes key point. Patterning of the new stacks containing these materials require both new plasma etch chemistries and new approaches.
We propose a BCl3/N2 based plasma mixture for the advanced gate patterning (in this case pure Ge gates and TaN metal gates). There are three reasons to select this combination:
a) The gas mixture generates Cl* species able to etch a diversity of materials, b) it is selective towards Si due to formation of passivating Si-B bonds and c) it improves profile control possibly by formation of a passivating BN-like film on feature side walls. It was found that BCl3 in presence of N2 results in a film deposition if no bias is applied to the substrate (i.e. there is no ion bombardment). The film is hexagonal BN-like since the characteristic peaks corresponding to the in-plane B-N and out-of-plane B-N-B bonds were found in FTIR spectra. The composition of the film surface as found by XPS is B, N and O (as no O2 is present in the plasma it may be a result of oxidation in the atmosphere), the amount of Cl is approx. 1%. The film is soluble in water that makes its removal easy. The deposition rate can be as high as 300 nm/min depending on plasma power, pressure, flow rates and BCl3 to N2 ratio.
We propose to use the BCl3/N2 mixture to etch materials too sensitive to Cl-based plasma. Pure BCl3 plasma might distort gate profiles, as materials are etched in a lateral direction as well, this is the case, e.g. for pure Ge gates. Addition of small amount of nitrogen (5% to 10%) to the BCl3 plasma preserves the vertical profile, apparently by the formation of a passivating BN-like layer on the vertical surfaces where there is no ion bombardment. Too high nitrogen concentration results in positively sloped gate profile or even in the etch stop that could be attributed to the too high deposition rate that exceeds the etch rate. All experiments have been performed in Lam Versys 2300 etch chamber.
Porous materials are being investigated as low dielectric constant (low-k) materials. While porosity decreases the k-value of a material by decreasing its density, it simultaneously allows unwanted adsorption and diffusion of chemicals inside the porous matrix. To investigate this, different porous low-k materials, specifically silicon oxycarbide (SiOCH), methylsilsesquioxane (MSQ), and a polymer, were exposed to polar (ethanol) and non-polar (toluene) solvents. A difference in diffusion of polar and non-polar solvents would be an indication of the density of polar centers which attract polar molecules (such as water) and increase the dielectric constant of a film. The diffusion coefficient for toluene at room temperature was found to be approximately 2×10-5 cm2/sec for MSQ (40% porosity), 10-7 cm2/sec for SiOCH (7% porosity), 2×10-8 cm2/sec for the polymer. The observed diffusion can be described by a model of a viscous flow in a porous medium. The toluene/ethanol diffusion coefficient ratios were 4.4, 1.3, 1 for MSQ, SiOCH, and the polymer, respectively. The difference in toluene/ethanol diffusion can potentially be used to screen a material's affinity for water adsorption.
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