Area-selective atomic layer deposition (ALD) is rapidly gaining interest because of its potential application in self-aligned fabrication schemes for next-generation nanoelectronics. Here, we introduce an approach for area-selective ALD that relies on the use of chemoselective inhibitor molecules in a three-step (ABC-type) ALD cycle. A process for area-selective ALD of SiO2 was developed comprising acetylacetone inhibitor (step A), bis(diethylamino)silane precursor (step B), and O2 plasma reactant (step C) pulses. Our results show that this process allows for selective deposition of SiO2 on GeO2, SiNx, SiO2, and WO3, in the presence of Al2O3, TiO2, and HfO2 surfaces. In situ Fourier transform infrared spectroscopy experiments and density functional theory calculations underline that the selectivity of the approach stems from the chemoselective adsorption of the inhibitor. The selectivity between different oxide starting surfaces and the compatibility with plasma-assisted or ozone-based ALD are distinct features of this approach. Furthermore, the approach offers the opportunity of tuning the substrate-selectivity by proper selection of inhibitor molecules.

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Area-selective atomic layer deposition (ALD) of ZnO was achieved on SiO 2 seed layer patterns on Hterminated silicon substrates, using diethylzinc (DEZ) as the zinc precursor and H 2 O as the coreactant. The selectivity of the ALD process was studied using in situ spectroscopic ellipsometry and scanning electron microscopy, revealing improved selectivity for increasing deposition temperatures from 100 to 300 °C. The selectivity was also investigated using transmission electron microscopy and energy-dispersive X-ray spectroscopy. Density functional theory (DFT) calculations were performed to corroborate the experimental results obtained and to provide an atomic-level understanding of the underlying surface chemistry. A kinetically hindered proton transfer reaction from the H-terminated Si was conceived to underpin the selectivity exhibited by the ALD process. By combining the experimental and DFT results, we suggest that the trend in selectivity with temperature may be due to a strong DEZ or H 2 O physisorption on the H-terminated Si that hampers high selectivity at low deposition temperature. This work highlights the deposition temperature as an extra process parameter to improve the selectivity.

Atomic layer deposition (ALD) is renowned for its step coverage in porous substrates. Several emerging applications require a combination of this high step coverage with high throughput ALD, like spatial ALD. Often, high throughput ALD is performed at atmospheric pressure, and therefore, the effect of reactor pressure on the saturation dose is investigated. ALD inside porous substrates is governed by three key parameters: the reaction probability, the pore aspect ratio, and the precursor diffusion coefficient, of which the latter one contains the reactor pressure dependency. The effect of these parameters on the saturation dose is validated using Monte Carlo modeling, where the reactor pressure dependency is included through the mean free path. A reaction-limited and a diffusion-limited regime can be identified, and it is shown that for many realistic experimental conditions, even at low reactor pressures, the saturation dose is in the diffusion-limited regime. An expression for the pressure dependent saturation dose in the diffusion-limited regime is derived. For small pore diameters, the saturation dose is pressure independent, but for larger pores, higher saturation doses are required for atmospheric reactor pressures than for low reactor pressures. However, as high reactor pressures enable much higher precursor partial pressures than low reactor pressures, the resulting saturation times can be much shorter at atmospheric pressure than low pressure. Often, high surface area porous substrates will lead to supply limited conditions, and increased saturation times have to be taken into account. These results show that the atmospheric pressure ALD can be used for high throughput ALD inside porous substrates, as long as high precursor partial pressures and molar flows can be applied. This is experimentally demonstrated by a near 100% step coverage obtained by atmospheric spatial ALD of alumina in high aspect ratio pores.

Implementation of vapor/phase dosing of small molecule inhibitors (SMIs) in advanced atomic layer deposition (ALD) cycles is currently being considered for bottom-up fabrication by area-selective ALD. When SMIs are used, it can be challenging to completely block precursor adsorption due to the inhibitor size and the relatively short vapor/phase exposures. Two strategies for precursor blocking are explored: (i) physically covering precursor adsorption sites, i.e., steric shielding, and (ii) eliminating precursor adsorption sites from the surface, i.e., chemical passivation. In this work, it is determined whether steric shielding is enough for effective precursor blocking during area-selective ALD or whether chemical passivation is required as well. At the same time, we address why some ALD precursors are more difficult to block than others. To this end, the blocking of the Al precursor molecules trimethylaluminum (TMA), dimethylaluminum isopropoxide (DMAI), and tris(dimethylamino)aluminum (TDMAA) was studied by using acetylacetone (Hacac) as inhibitor. It was found that DMAI and TDMAA are more easily blocked than TMA because they adsorb on the same surface sites as Hacac, while TMA is also reactive with other surface sites. This work shows that chemical passivation plays a crucial role for precursor blocking in concert with steric shielding. Moreover, the reactivity of the precursor with the surface groups on the non-growth area dictates the effectiveness of blocking precursor adsorption.