Area-selective Atomic Layer Deposition Research Articles

Preparation of Br-terminated Si(100) and Si(111) surfaces and their use as atomic layer deposition resists

In area-selective processes, such as area-selective atomic layer deposition (AS-ALD), there is renewed interest in designing surface modification schemes allowing to tune the reactivity of the nongrowth (NG) substrates. Many efforts are directed toward small molecule inhibitors or atomic layers, which would modify selected surfaces to delay nucleation and provide NG properties in the target AS-ALD processes allowing for the manufacturing of smaller sized features than those produced with alternative approaches. Bromine termination of silicon surfaces, specifically Si(100) and Si(111), is evaluated as a potential pathway to design NG substrates for the deposition of metal oxides, and TiO2 (from cycles of sequential exposures of tetrakis-dimethylamido-titanium and water) is tested as a prototypical deposition material. Nucleation delays on the surfaces produced are comparable to those on H-terminated silicon that is commonly used as an NG substrate. However, the silicon surfaces produced by bromination are more stable, and even oxidation does not change their chemical reactivity substantially. Once the NG surface is eventually overgrown after a large number of ALD cycles, bromine remains at the interface between silicon and TiO2. The NG behavior of different crystal faces of silicon appears to be similar, albeit not identical, despite different arrangements and coverage of bromine atoms.

Area-Selective Atomic Layer Deposition of Ruthenium via Reduction of Interfacial Oxidation

Area-Selective Atomic Layer Deposition of Ruthenium via Reduction of Interfacial Oxidation

Mechanisms of Area-Selective Atomic Layer Deposition and Their Impact on Feature Sizes

Mechanisms of Area-Selective Atomic Layer Deposition and Their Impact on Feature Sizes

An Atomistic Picture of Buildup and Degradation Reactions in Area-Selective Atomic Layer Deposition with a Small Molecule Inhibitor

An Atomistic Picture of Buildup and Degradation Reactions in Area-Selective Atomic Layer Deposition with a Small Molecule Inhibitor

Area-Selective Atomic Layer Deposition of Ru Using Carbonyl-Based Precursor and Oxygen Co-Reactant: Understanding Defect Formation Mechanisms.

Area selective deposition (ASD) is a promising IC fabrication technique to address misalignment issues arising in a top-down litho-etch patterning approach. ASD can enable resist tone inversion and bottom-up metallization, such as via prefill. It is achieved by promoting selective growth in the growth area (GA) while passivating the non-growth area (NGA). Nevertheless, preventing undesired particles and defect growth on the NGA is still a hurdle. This work shows the selectivity of Ru films by passivating the Si oxide NGA with self-assembled monolayers (SAMs) and small molecule inhibitors (SMIs). Ru films are deposited on the TiN GA using a metal-organic precursor tricarbonyl (trimethylenemethane) ruthenium (Ru TMM(CO)3) and O2 as a co-reactant by atomic layer deposition (ALD). This produces smooth Ru films (<0.1 nm RMS roughness) with a growth per cycle (GPC) of 1.6 Å/cycle. Minimizing the oxygen co-reactant dose is necessary to improve the ASD process selectivity due to the limited stability of the organic molecule and high reactivity of the ALD precursor, still allowing a Ru GPC of 0.95 Å/cycle. This work sheds light on Ru defect generation mechanisms on passivated areas from the detailed analysis of particle growth, coverage, and density as a function of ALD cycles. Finally, an optimized ASD of Ru is demonstrated on TiN/SiO2 3D patterned structures using dimethyl amino trimethyl silane (DMA-TMS) as SMI.

Enhanced Deposition Selectivity of High-k Dielectrics by Vapor Dosing and Selective Removal of Phosphonic Acid Inhibitors.

Area-selective atomic layer deposition (AS-ALD), which provides a bottom-up nanofabrication method with atomic-scale precision, has attracted a great deal of attention as a means to alleviate the problems associated with conventional top-down patterning. In this study, we report a methodology for achieving selective deposition of high-k dielectrics by surface modification through vapor-phase functionalization of octadecylphosphonic acid (ODPA) inhibitor molecules accompanied by post-surface treatment. A comparative evaluation of deposition selectivity of ZrO2 thin films deposited with the O2 and O3 reactants was performed on SiO2, TiN, and W substrates, and we confirmed that high enough deposition selectivity over 10 nm can be achieved even after 200 cycles of ALD with the O2 reactant. Subsequently, the electrical properties of ZrO2 films deposited with O2 and O3 reactants were investigated with and without post-deposition treatment. We successfully demonstrated that high-quality ZrO2 thin films with high dielectric constants and stable antiferroelectric properties can be produced by subjecting the films to ozone, which can eliminate carbon impurities within the films. We believe that this work provides a new strategy to achieve highly selective deposition for AS-ALD of dielectric on dielectric (DoD) applications toward upcoming bottom-up nanofabrication.

Si precursor inhibitors for area selective deposition of Ru

Area-selective atomic layer deposition (AS-ALD) using highly process-compatible precursor inhibitors (PIs) has garnered attention because of the need to overcome three-dimensional nanofabrication bottlenecks. The main advantages of precursor inhibitor (PI) molecules are their high process compatibility and their inherent bifunctionality as inhibitors and precursors. Herein, we examined the inhibition properties, adsorption mechanisms, and adsorption configurations of two PIs, bis(N,N-dimethylamino)dimethylsilane (PI1) and tris(dimethylamino)silane (PI2). Both PIs selectively inhibited the SiO2 surface but not the Cu surface, which enabled the AS-ALD of Ru films on the latter. The inhibition mechanisms were elucidated on the basis of chemical reactivity and steric hindrance considerations using density functional theory calculations and Monte Carlo simulations. PI1 featured a larger areal coverage than PI2 because of the favorable adsorption configuration of the former, inducing a stronger steric hindrance effect and achieving a higher inhibition performance against Ru ALD, although the two PIs had similar chemical reactivities toward the examined surface. Furthermore, PI1 and PI2 formed SiO2 ALD films when ozone was used as a reactant. The differences in the growth characteristics of the corresponding ALD SiO2 films were explained by the different adsorption configurations of PIs. Thus, our work elucidates the adsorption configurations of silane-based PIs and thus paves the way for the more effective utilization of their bifunctionality, inhibition properties, and growth characteristics in future AS-ALD processes.

Adsorption of dimethylaluminum isopropoxide (DMAI) on the Al2O3 surface: A machine-learning potential study

Dimethylaluminum isopropoxide (DMAI) is attracting attention as an alternative precursor for atomic layer deposition (ALD) of aluminum oxide (Al2O3). However, the surface chemical reaction mechanisms of DMAI during ALD regarding its dimeric structure under vacuum deposition process conditions has yet to be clear. In this work, the adsorption mechanism of dimeric and monomeric DMAI on a fully hydroxylated Al2O3 surface is studied using machine-learning potential (MLP) calculations. The initial adsorption of DMAI appears facile and would result in the coexistence of both methyl and isopropoxy ligands on the surface. The reactivity of DMAI is smaller than that of TMA, owing to the propensity of DMAI to adopt a dimeric form. Especially when the substrate is partially covered by other adsorbate species, the large molecular size and low reactivity of dimeric DMAI considerably hinder its reactivity toward surface adsorption. Current results are in good correspondence with the previous experimental results, where lower growth per cycle (GPC) and higher selectivity in area-selective ALD (AS-ALD) could be observed by using DMAI than compared to those of TMA processes.

In situ formation of inhibitor species through catalytic surface reactions during area-selective atomic layer deposition of TaN.

Small molecule inhibitors (SMIs) have been gaining attention in the field of area-selective atomic layer deposition (ALD) because they can be applied in the vapor-phase. A major challenge for SMIs is that vapor-phase application leads to a disordered inhibitor layer with lower coverage as compared to self-assembled monolayers, SAMs. A lower coverage of SMIs makes achieving high selectivity for area-selective ALD more challenging. To overcome this challenge, mechanistic understanding is required for the formation of SMI layers and the resulting precursor blocking. In this study, reflection adsorption infrared spectroscopy measurements are used to investigate the performance of aniline as an SMI. Our results show that aniline undergoes catalytic surface reactions, such as hydrogenolysis, on a Ru non-growth area at substrate temperatures above 250 °C. At these temperatures, a greatly improved selectivity is observed for area-selective TaN ALD using aniline as an inhibitor. The results suggest that catalytic surface reactions of the SMI play an important role in improving precursor blocking, likely through the formation of a more carbon-rich inhibitor layer. More prominently, catalytic surface reactions can provide a new strategy for forming inhibitor layers that are otherwise very challenging or impossible to form directly through vapor-phase application.

Selective nitride passivation using vapor-dosed aldehyde inhibitors for area-selective atomic layer deposition

We present a methodology for achieving selective deposition of Ru films through surface modification via vapor-phase functionalization of aldehyde inhibitor molecules. We conduct a comparative evaluation of the blocking capability using vapor-dosing of two different types of aldehyde molecules: undecylaldehyde and benzaldehyde as aliphatic and aromatic ring inhibitors, respectively, on W, TiN, SiN, and SiO2 substrates. By adjusting the vapor-process conditions of both aldehydes, we confirm chemo-selective adsorption on nitride surfaces, resulting in significant growth retardation during subsequent Ru atomic layer deposition. Under optimized conditions for achieving nitride versus oxide selectivity, we successfully demonstrated area-selective atomic layer deposition (AS-ALD) of Ru films on patterned-TiN/SiO2 substrates.

Blocking mechanisms in area-selective ALD by small molecule inhibitors of different sizes: Steric shielding versus chemical passivation

Small molecule inhibitors (SMIs) hold great promise for area-selective deposition due to their vapor-phase application being compatible with industrial processing. However, to date only a handful of SMIs have been studied, and the mechanisms of precursor blocking require further understanding. In this study, we explore the inhibition of SiO2 ALD on Al2O3 surfaces comparing three SMIs of different sizes: acetic acid (HAc), acetylacetone (Hacac), and 2,2,6,6-tetramethyl-3,5-heptanedione (Hthd). The goal is to unravel the contributions of two important factors to their blocking performance: steric shielding, i.e. physically covering reactive surface sites, and chemical passivation, i.e. chemically consuming surface reactive sites. Experimentally, it is found that HAc and Hthd outperform the previously studied Hacac, as revealed by longer nucleation delays on Al2O3 from in-situ spectroscopic ellipsometry, and by enhanced Si precursor blocking inferred from in-situ infrared spectroscopy. Through density functional theory and random sequential adsorption simulations, we illustrate that varying the size of SMIs brings benefits from either higher steric shielding or better chemical passivation. As compared to Hacac, HAc performs better due to its smaller size, yielding denser packing and thus higher chemical passivation. Hthd on the other hand, benefits from its bulkiness with a higher contribution from steric shielding.

HfO2 Area-Selective Atomic Layer Deposition with a Carbon-Free Inhibition Layer

HfO₂ Area-Selective Atomic Layer Deposition with a Carbon-Free Inhibition Layer

Area-selective atomic layer deposition of Ru thin films by chemo-selective inhibition of alkyl aldehyde molecules on nitride surfaces

Area-selective atomic layer deposition (AS-ALD) on pre-defined areas is of crucial importance nowadays in significantly reducing complexities associated with current top-down fabrication processes. In this work, we report the effects of surface modification using various alkyl aldehyde inhibitors with different chain lengths—hexanal, decanal, and undecanal—on nitride surfaces such as TiN and SiN to achieve AS-ALD. On the basis of density functional theory calculations and experimental analysis, including water contact angle and X-ray photoelectron spectroscopy, it is evident that aldehydes would chemo-selectively react with the –NH2 functional groups present on the nitride surfaces. Then, we further investigate their blocking ability against subsequent Ru ALD, a promising next-generation electrode material. It is worth noting that the Ru deposition thickness decreased by 4–10 nm with the presence of undecanal adsorbed on SiN and TiN substrates. Finally, we successfully demonstrate AS-ALD of Ru thin films over 8 nm on a patterned TiN/SiO2 substrate. These results hold potential for applications in bottom-up nanofabrication techniques for next-generation nanoelectronic applications.

Area-selective atomic layer deposition (AS-ALD) of low temperature (300 °C) cobalt thin film using octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs)

As the semiconductor industry advances, manufacturing technologies encounter challenges in achieving precise alignment and thickness control with smaller and more intricate 3D structures. Addressing this, Area-selective atomic layer deposition (AS-ALD) emerges as a promising “bottom-up” approach, offering an alternative to current nano-patterning techniques. To achieve AS-ALD, self-assembled monolayers (SAMs) are employed as inhibitor agents. In this study, we employed plasma-enhanced atomic layer deposition (PEALD) to promote self-limiting surface reactions and enable low-temperature processing, thereby facilitating the implementation of high purity cobalt (Co) film through AS-ALD using octadecyltrichlorosilane (ODTS) SAM as an inhibitor. The selective deposition is achieved by employing SAMs as an inhibitor, belonging to the deactivation process, a common method for realizing a bottom-up approach. SAMs can form a thin organic film on a solid surface, allowing for surface modifications to become hydrophobic or hydrophilic. Through the selective deposition of Co in the PEALD low-temperature process (300 °C), we successfully addressed the degradation issue of ODTS SAM and verified the successful achievement of a high-purity selectively deposited 13.4 nm Co film. Our findings highlight the potential of selective Co deposition for realizing complex 3D structures and narrow interconnection layers.

Highly area-selective atomic layer deposition of device-quality Hf1-xZrxO2 thin films through catalytic local activation

Area-selective atomic layer deposition (AS-ALD) has garnered significant attention as a promising bottom-up patterning process for sub-10 nm scale technology, offering unmatched atomic-scale precision and pattern alignment capabilities in 3D nanofabrication. In this study, we present a groundbreaking methodology for achieving highly selective deposition of Hf1-xZrxO2 (HZO) thin films through catalytic local activation on noble metal surfaces (Ru and Pt) and TiN surfaces, without the need for surface inhibitory materials. To achieve inherent selectivity on metal surfaces, we employ O2 gas as a mildly oxidizing reactant and utilize cyclopentadienyl-tris(dimethylamido)-hafnium(zirconium) [Hf(Zr)Cp(NMe2)3] precursors, which require strong oxidizing agents, for HZO film formation. By catalytically dissociating O2 molecules, we successfully achieved area-selective deposition of HZO films greater than ∼7 nm on both blanket Ru versus Si substrates and Pt/Si-patterned substrates. Furthermore, we demonstrate the selective deposition of antiferroelectric HZO thin films with high dielectric constants of 34 and 31 on Ru and TiN substrates, respectively, using the inherent AS-ALD method combined with post-ozone treatment. Importantly, this catalytic local activation approach for achieving inherent deposition selectivity expands the potential utility of 3D bottom-up nanopatterning processes in next-generation nanoelectronic applications.

Area-selective atomic layer deposition on 2D monolayer lateral superlattices

The advanced patterning process is the basis of integration technology to realize the development of next-generation high-speed, low-power consumption devices. Recently, area-selective atomic layer deposition (AS-ALD), which allows the direct deposition of target materials on the desired area using a deposition barrier, has emerged as an alternative patterning process. However, the AS-ALD process remains challenging to use for the improvement of patterning resolution and selectivity. In this study, we report a superlattice-based AS-ALD (SAS-ALD) process using a two-dimensional (2D) MoS2-MoSe2 lateral superlattice as a pre-defining template. We achieved a minimum half pitch size of a sub-10 nm scale for the resulting AS-ALD on the 2D superlattice template by controlling the duration time of chemical vapor deposition (CVD) precursors. SAS-ALD introduces a mechanism that enables selectivity through the adsorption and diffusion processes of ALD precursors, distinctly different from conventional AS-ALD method. This technique facilitates selective deposition even on small pattern sizes and is compatible with the use of highly reactive precursors like trimethyl aluminum. Moreover, it allows for the selective deposition of a variety of materials, including Al2O3, HfO2, Ru, Te, and Sb2Se3.

Unfolding an Elusive Area-Selective Deposition Process: Atomic Layer Deposition of TiO2 and TiON on SiN vs SiO2.

Area-selective atomic layer deposition (AS-ALD) processes for TiO2 and TiON on SiN as the growth area vs SiO2 as the nongrowth area are demonstrated on patterns created by state-of-the-art 300 mm semiconductor wafer fabrication. The processes consist of an in situ CF4/N2 plasma etching step that has the dual role of removing the SiN native oxide and passivating the SiO2 surface with fluorinated species, thus rendering the latter surface less reactive toward titanium tetrachloride (TiCl4) precursor. Additionally, (dimethylamino)trimethylsilane was employed as a small molecule inhibitor (SMI) to further enhance the selectivity. Virtually perfect selectivity was obtained when combining the deposition process with intermittent CF4/N2 plasma-based back-etching steps, as demonstrated by scanning and transmission electron microscopy inspections. Application-compatible thicknesses of ∼8 and ∼5 nm were obtained for thermal ALD of TiO2 and plasma ALD of TiON.

Organosulfide Inhibitor Instigated Passivation of Multiple Substrates for Area-Selective Atomic Layer Deposition of HfO2

Organosulfide Inhibitor Instigated Passivation of Multiple Substrates for Area-Selective Atomic Layer Deposition of HfO₂

Understanding the role of carboxylic acid surfactants in the growth inhibition effect during area-selective atomic layer deposition: the case of ZnO growth on Cu and Cu2O.

Herein, we report a detailed adsorption process of acetic acid (AA) as a model for the head group of carboxylic acid self-assembled monolayers on Cu and Cu2O (111) surfaces and the effect of diethyl zinc (DEZ) on its adsorption geometry on Cu2O (111) using quantum chemical calculations. The most stable adsorption configurations were obtained considering electrostatic potential compatibility from the molecule and surface. Overall, the adsorption behavior revealed bidentate binding as the most stable configuration. Weak van der Waals interactions are key in AA adsorption on Cu (111), while in Cu2O (111), coordination and hydrogen bonds dominated the interaction. AA adsorption geometry on Cu2O revealed that DEZ has no significative impact on the carbonyl-chemisorbed AA and bidentate adsorption modes. These results highlight the significance of the different adsorption modes for achieving area-selective deposition using atomic layer deposition and soft removal SAM molecules.

Machine Learning Modeling and Run-to-Run Control of an Area-Selective Atomic Layer Deposition Spatial Reactor

Semiconducting materials require stringent design specifications that make their fabrication more difficult and prone to flaws that are costly and damaging to their computing and electrical properties. Area-selective atomic layer deposition is a process that addresses concerns associated with design imperfections but requires substantial monitoring to ensure that process regulation is maintained. This work proposes a run-to-run controller with an exponentially weighted moving average method for an area-selective atomic layer deposition rotary reactor by adjusting the rotation speed of the substrate to control the growth per cycle of the wafer, which is calculated through a multiscale model with machine learning integration for pressure field generation and kinetic Monte Carlo simulations to increase computational efficiency. Results indicate that the run-to-run controller was able to bring the process to the setpoint when subjected to moderate pressure and kinetic shift disturbances.