Volume 34, Issue 1, January 2016
Index of content:
- Atomic Layer Deposition (ALD)
Thermal chemistry of copper acetamidinate atomic layer deposition precursors on silicon oxide surfaces studied by XPS34(2016); http://dx.doi.org/10.1116/1.4927843View Description Hide Description
The thermal surface chemistry of copper(I)-N,N′-di-sec-butylacetamidinate, [Cu( sBu-amd)]2, a metalorganic complex recently proposed for the chemical-based deposition of copper films, has been characterized on SiO2 films under ultrahigh vacuum conditions by x-ray photoelectron spectroscopy (XPS). Initial adsorption at cryogenic temperatures results in the oxidation of the copper centers with Cu 2p3/2 XPS binding energies close to those seen for a +2 oxidation state, an observation that the authors interpret as the result of the additional coordination of oxygen atoms from the surface to the Cu atoms of the molecular acetamidinate dimer. Either heating to 300 K or dosing the precursor directly at that temperature leads to the loss of one of its two ligands, presumably via hydrogenation/protonation with a hydrogen/proton from a silanol group, or following a similar reaction on a defect site. By approximately 500 K the Cu 2p3/2, C 1s, and N 1s XPS data suggest that the remaining acetamidinate ligand is displaced from the copper center and bonds to the silicon oxide directly, after which temperatures above 900 K need to be reached to promote further (and only partial) decomposition of those organic moieties. It was also shown that the uptake of the Cu precursor is self-limiting at either 300 or 500 K, although the initial chemistry is somewhat different at the two temperatures, and that the nature of the substrate also defines reactivity, with the thin native silicon oxide layer always present on Si(100) surfaces being less reactive than thicker films grown by evaporation, presumably because of the lower density of surface nucleation sites.
Comparison of B2O3 and BN deposited by atomic layer deposition for forming ultrashallow dopant regions by solid state diffusion34(2016); http://dx.doi.org/10.1116/1.4928705View Description Hide Description
In this study, the authors investigated atomic layer deposition (ALD) of B2O3 and BN for conformal, ultrashallow B doping applications and compared the effect of dopant-containing overlayers on sheet resistance (Rs) and B profiles for both types of films subjected to a drive-in thermal anneal. For the deposition of B2O3, tris(dimethylamido)borane and O3 were used as coreactants and for the deposition of BN, BCl3 and NH3 were used as coreactants. Due to the extreme air instability of B2O3 films, physical analysis was performed on B2O3 films, which were capped in-situ with ∼30 Å ALD grown Al2O3 layers. For the BN films, in-situ ALD grown Si3N4 capping layers (∼30 Å) were used for comparison. From spectroscopic ellipsometry, a thickness decrease was observed after 1000 °C, 30 s anneal for the B2O3 containing stack with 60 ALD cycles of B2O3, whereas the BN containing stacks showed negligible thickness decrease after the annealing step, regardless of the number of BN cycles tested. The postanneal reduction in film thickness as well as decrease in Rs for the B2O3 containing stack suggests that the solid state diffusion dopant mechanism is effective, whereas for the BN containing stacks this phenomenon seems to be suppressed. Further clarification of the effectiveness of the B2O3 containing layer compared to the film stacks with BN was evidenced in backside secondary ion mass spectrometry profiling of B atoms. Thus, B2O3 formed by an ALD process and subsequently capped in-situ followed by a drive-in anneal offers promise as a dopant source for ultrashallow doping, whereas the same method using BN seems ineffective. An integrated approach for B2O3 deposition and annealing on a clustered tool also demonstrated controllable Rs reduction without the use of a capping layer.