The exceptional thickness control (atomic scale) and conformality (uniformity over nanoscale 3D features) of atomic layer deposition (ALD) has made it the process of choice for numerous applications from microelectronics to nanotechnology, and for a wide variety of ALD processes and resulting materials. While its benefits derive from self-terminated chemisorbed reactions of alternatively supplied gas precursors, identifying a suitable process window in which ALD's benefits are realized can be a challenge, even in favorable cases.

In this work, a strategy exploiting in-situ gas phase sensing in conjunction with ex-situ measurements of the film properties at the wafer scale is employed to explore and optimize the prototypical Al2O3 ALD process. Downstream mass-spectrometry is first used to rapidly identify across the [H2O x Al(CH3)3] process space the exposure conditions leading to surface saturation. The impact of precursor doses outside as well as inside the parameter space outlined by mass-spectrometry is then investigated by characterizing film properties across 100 mm wafer using spectroscopic ellipsometry, CV and IV electrical characterization, XPS and SIMS.

Under ideal dose conditions, excellent thickness uniformity was achieved (1sigma/mean<1%) in conjunction with a deposition rate and electrical properties in good agreement with best literature data. As expected, under-dosing of precursor results in depletion of film growth in the flow direction across the wafer surface. Since adsorbed species are reactive with respect to subsequent dose of the complementary precursor, such depletion magnifies non-uniformities as seen in the cross-flow reactor, thereby decorating deviations from a suitable ALD process recipe. Degradation of the permittivity and leakage current density across the wafer was observed though the film composition remained unchanged. Upon higher water dose in the over-exposure regime, deposition rates increased by up to 40% while the uniformity degraded. In contrast, overdosing of TMA and ozone (used for comparison to water) did not affect the process performances. These results point to complex saturation dynamics of water dependent on partial pressure and potential multilayer adsorption caused by hydrogen-bonding.