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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.
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.
In this paper, we have studied the segregation phenomenon of Cu on the surfaces of patterned lines, dry-etched films and non-etched films, by using X-ray photoelectron spectroscopy and lower energy Rutherford Backscattering Spectrometry. Significant enrichment of Cu is found on the sidewall of the lines. Annealing at 350°C and above cause the disappearance of this enrichment. Origin and evolution of this Cu enrichment have been investigated on films taken out from different steps of the etching process. It has been found that most of the Cu products induced by the plasma etching are CuCl and CuCl2 and they are removed mostly from the top Al oxide layer by the strip process. On the interface area between Al and the native oxide, considerable quantities of etched induced Cu are retained. This Cu is identified to be mainly metallic Cu. Different from the mechanism explained above, thermal annealing can also cause Cu segregation. We have found that Cu atoms diffuse into the native Al oxide where they form Cu2O.
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