Atomic Layer Deposition Of HfO2 Research Articles

Operando study of HfO2 atomic layer deposition on partially hydroxylated Si(111)

The introduction of atomic layer deposition (ALD), to the microelectronics industry has introduced a large number of new possible materials able to be deposited in layers with atomic thickness control. One such material is the high-κ oxide HfO2; thermally stable and ultrathin HfO2 films deposited by ALD are a significant contender to replace SiO2 as the gate oxide in capacitor applications. We present a mechanistic study of the first deposition cycle of HfO2 on the Si(111) surface using tetrakis(dimethylamido) hafnium (TDMAHf) and water as precursors using operando ambient pressure x-ray photoelectron spectroscopy. Here, we show that the hydroxylation of the clean Si(111) surface by residual water vapor, resulting in a 0.3 monolayer coverage of hydroxyls, leads to instantaneous full surface coverage of TDMAHf. The change in the atomic ratio of Hf to C/N found during the first deposition half-cycle, however, does not match the assumed immediate ligand loss through reaction with surface hydroxyls. One would expect an immediate loss of ligands, indicated by a Hf:N ratio of approximately 1:3 as TDMAHf deposits onto the surface; however, a Hf:N ratio of 1:3.6 is observed. The partial hydroxylation on the Si(111) surface leads to binding through the TDMAHf ligand N atoms resulting in both N and CH3 being found remaining on the surface post water half-cycle. Although there is evidence of ligand exchange reactions occurring at Si–OH sites, it also seems that N binding can occur on bare Si, highlighting the complexity of the substrate/precursor reaction even when hydroxyls are present. Moreover, the initial low coverage of Si–OH/Si–H appears to severely limit the amount of Hf deposited, which we hypothesize is due to the specific geometry of the initial arrangement of Si–OH/Si–H on the rest- and adatoms.

(Invited) Enabling High Quality Dielectric Passivation on Monolayer WS2 Using a Sacrificial Graphene Oxide Template

Two-dimensional transition metal dichalcogenides (2D TMDC’s) hold a wide variety of applications, among which microelectronic devices. 2D TMDC’s are promising alternatives for today’s silicon-based technology but suffer from various integration challenges. Among others, direct dielectric growth on the 2D surface occurs poorly due to their self-passivated surfaces resulting in island-like growth initiated at defect sites. This work focuses on enabling uniform high-k dielectric nucleation and growth on 2D TMDC’s via a sacrificial, graphene oxide-based buffer layer. Essentially, the role of the sacrificial graphene buffer layer is twofold: 1) serve as a passivation layer, protecting the underlying 2D TMDC (i.e., WS2) during processing and 2) act as a nucleation layer, enabling uniform atomic layer deposition (ALD) high-k dielectric (i.e,. HfO2) growth. A graphene layer is transferred on monolayer WS2, after which polymeric transfer residues are cleaned via a combination of wet treatments and a dry hydrogen downstream plasma exposure. The cleaned graphene is functionalized via a dry UV/O3 oxidative treatment, which enriches its basal plane with carbon-oxygen single bond functionalities by sacrificing its π-network. This way, the graphene carbon lattice itself remains intact and retains its passivation properties. Moreover, a substrate dependency is observed where graphene transferred on WS2 requires longer UV/O3 exposure to ensure functionalization compared to a SiO2 substrate and can be explained by UV-light induced, ultrafast charge transfer between the graphene and WS2 monolayer. The carbon-oxygen groups formed on graphene’s basal plane act as nucleation sites during a subsequent HfO2 ALD process. A constant roughness is noted for the HfO2 film grown on the graphene oxide capped WS2, indicating uniform material deposition even in the early stages of the ALD process. This is in sharp contrast when HfO2 is directly grown on the WS2 monolayer, whose roughness stabilizes only after many ALD cycles (up to 256), demonstrating the poor, island-like growth mechanism. In addition, a similar hafnium areal density is measured for the graphene oxide capped WS2 compared bare SiO2, which was selected to represent a well-functionalized surface and thus confirming the efficiency of the graphene oxide-based nucleation layer. For devices incorporating the graphene oxide buffer layer concept, a crucial question is to what extent the graphene oxide layer gives rise to leakage currents by providing a conductive path between source and drain. Electrical evaluation of a GFET by means of I-V measurements reveal a significant shift in Dirac point towards positive gate voltage for transferred graphene, which is typically associated with p-type doping originating from the polymeric transfer residues still present on the surface. The Dirac point shifts towards 0-point voltage after final hydrogen downstream plasma cleaning, confirming the effectiveness of the established cleaning protocol. Moreover, Graphene’s conductivity is suppressed after UV/O3 to the nA range, as caused by the formation of carbon-oxygen functionalities and associated sacrifice of its π-network. The residual current may be further suppressed by extending the UV/O3 treatment, but nevertheless demonstrates that the graphene oxide buffer layer will not give rise to significant leakage currents.

Atomic Layer Deposition of HfAlOx for High-k Gate Dielectrics

Nowadays, the downscaling of CMOS devices requires continued effort to propose high performance components with extremely compact size. Surely, this trend is not achievable without extremely enhanced High-k gate stack materials, inter alia. For years, HfO2-based dielectrics deposited using ALD (Atomic Layer Deposition) technique are perfect dielectrics of choice for various devices and applications (Memristor, resistive random access memory, ferroelectric random access memory, antiferrolectric capacitances, ferroelectric FET...).As such, HfAlOx films present a good compromise between HfO2 and Al2O3 in term of coupling properties and insulating capabilities in comparison with both single HfO2 and Al2O3 films. The purpose of this work is to evaluate binary high-k HfAlOx dielectrics deposited by ALD technique. ALD is well suited for deposition of ultrathin films with exceptional capabilities enabling precise thickness, stoichiometry control and conformal growth at atomic scale. In this work, we focused on Al2O3/HfO2 films fabricated using two approaches: (i) repeatedly alternating the deposition of two different and separate extremely thin oxides (Al2O3 and HfO2; particular focus on HfO2/Al2O3/HfO2/Al2O3/HfO2 multilayer stack with equivalent Al fraction around 30%); (ii) combination of ALD super cycles allowing the formation HfAlOx layers. We analyze the general performance and the behavior of the binary high-k HfAlOx dielectrics (10 nm thin layers deposited at 300°C using TiCl4-TMA-H2O precursors) using physico-chemical (X-ray photoelectron spectroscopy XPS, X-ray reflectometry XRR, wavelength dispersive X-ray fluorescence WDXRF) and electrical measurements (Hg probe measurements, MIM capacitance).The incorporation of Al2O3 in the composition of the HfO2 gate dielectrics allows a perfect monitoring of physico-chemical properties varying from HfO2 layers to Al2O3 layers by controlling the number of Al2O3 and HfO2 ALD cycles. In this respect, we were able to monitor the Al fraction in the range of 5% to ~86% in the mixed binary dielectrics (Figure 1: XRR density of mixed binary layers vs Al/[Al+Hf] ratio, Figure 2: Al and Hf fractions in the mixed layer determined by WDXRF and XPS analysis).The electrical characteristics of the HfAlOx dielectrics confirm the influence of the Al fraction in the HfO2 layer. The leakage currents of the mixed layers decreases with increasing the Al fraction (Figure 3: J/E characteristics of mixed and stacked HfAlOx layers). The breakdown voltages for all mixed HfAlOx layers are greater than that of reference HfO2 layer. On the other hand, the shown multilayer presents an intermediate leakage currents profiles between the two mixed HfAlOx (25%Al and 40%Al). Thus, the incorporation of Al in the construction of HfAlOx system is likely to decrease the number of defects. Furthermore, the fully integrated MIM structures exhibit areal capacitance in the range 10-15 nF/mm2 of ALD-based high-k HfAlOx (10 to 12 nm) depending on the Al fraction. Thus, ALD-HfAlOx with various composition highlight the potential tremendous for high-κ capacitances stack for CMOS semiconductor devices. Figure 1

Computer Modeling of Plasma-Enhanced Atomic Layer Deposition of HfO2 and ZrO2

Computer Modeling of Plasma-Enhanced Atomic Layer Deposition of HfO2 and ZrO2

Reduced leakage current in atomic-layer-deposited HfO2 thin films deposited at low temperature by in-situ defect passivation

HfO2 films grown via atomic layer deposition (ALD) at low temperature generally exhibit high impurity content, reduced density, and increased oxygen defects, resulting in degraded electrical properties. To overcome this issue, this study applied an in-situ defect passivation technique at low temperature, modifying the ALD oxygen source feeding step to suit heat-sensitive substrates. The electrical properties of the ALD HfO2 film grown at 80 °C are improved when the oxygen source feeding step is repeated twice, and especially the leakage current density is significantly decreased, which is approximately 1/7 smaller at an electric field of 1 MV/cm compared to the film grown via the conventional ALD process at 80 °C. This improvement in the electrical properties can be attributed to decreased carbon impurities and oxygen defects and increased film density. A simple modification of the oxygen source feeding step during the ALD process can effectively reduce defects within the ALD HfO2 films at the atomic layer level, even when grown at low deposition temperatures.

All‐Around HfO2 Stressor for Tensile Strain in GeSn‐on‐Insulator Nanobeam Lasers

AbstractTensile strained GeSn alloys are considered a key enabler for the realization of complementary metal‐oxide‐semiconductor laser sources. However, the tensile strained GeSn lasers reported to date require complex fabrication processes for applying tensile strain in GeSn, preventing tensile GeSn lasers from becoming the mainstream technology for integrated photonics. Here, a unique strain engineering method is presented that can introduce a uniform tensile strain in GeSn lasers by harnessing a widely developed atomic layer deposition (ALD) process. 1D photonic crystal nanobeam lasers under homogenous tensile strain induced by an ALD HfO2 all‐around stressor layer show a single‐mode lasing peak with a ≈31 nm redshift and ≈2 times intensity increase. The lasing threshold of tensile strained GeSn lasers is ≈12% improved compared to the unstrained GeSn lasers. It is believed that the approach offers a new path toward the realization of practical group‐IV laser sources for photonic‐integrated circuits.

N-Polar GaN Deep Recess HEMT With Atomic Layer Deposition HfO2 as Gate Insulator

N-Polar GaN Deep Recess HEMT With Atomic Layer Deposition HfO₂ as Gate Insulator

Preparation of Remote Plasma Atomic Layer-Deposited HfO2 Thin Films with High Charge Trapping Densities and Their Application in Nonvolatile Memory Devices.

Optimization of equipment structure and process conditions is essential to obtain thin films with the required properties, such as film thickness, trapped charge density, leakage current, and memory characteristics, that ensure reliability of the corresponding device. In this study, we fabricated metal-insulator-semiconductor (MIS) structure capacitors using HfO2 thin films separately deposited by remote plasma (RP) atomic layer deposition (ALD) and direct-plasma (DP) ALD and determined the optimal process temperature by measuring the leakage current and breakdown strength as functions of process temperature. Additionally, we analyzed the effects of the plasma application method on the charge trapping properties of HfO2 thin films and properties of the interface between Si and HfO2. Subsequently, we synthesized charge-trapping memory (CTM) devices utilizing the deposited thin films as charge-trapping layers (CTLs) and evaluated their memory properties. The results indicated excellent memory window characteristics of the RP-HfO2 MIS capacitors compared to those of the DP-HfO2 MIS capacitors. Moreover, the memory characteristics of the RP-HfO2 CTM devices were outstanding as compared to those of the DP-HfO2 CTM devices. In conclusion, the methodology proposed herein can be useful for future implementations of multiple levels of charge-storage nonvolatile memories or synaptic devices that require many states.

Atomic Layer Deposition of HfO2 Films Using TDMAH and Water or Ammonia Water.

Atomic layer deposition of HfO2 from TDMAH and water or ammonia water at different temperatures below 400 °C is studied. Growth per cycle (GPC) has been recorded in the range of 1.2-1.6 Å. At low temperatures (≤100 °C), the films grew faster and are structurally more disordered, amorphous and/or polycrystalline with crystal sizes up to 29 nm, compared to the films grown at higher temperatures. At high temperatures of 240 °C, the films are better crystallized with crystal sizes of 38-40 nm but grew slower. GPC, dielectric constant, and crystalline structure are improved by depositing at temperatures above 300 °C. The dielectric constant value and the roughness of the films have been determined for monoclinic HfO2, a mixture of orthorhombic and monoclinic, as well as for amorphous HfO2. Moreover, the present study shows that the increase in the dielectric constant of the films can be achieved by using ammonia water as an oxygen precursor in the ALD growth. The detailed investigations of the relationship between HfO2 properties and growth parameters presented here have not been reported so far, and the possibilities of fine-tuning and controlling the structure and performance of these layers are still being sought.

Dispersion Engineering of Waveguide Microresonators by the Design of Atomic Layer Deposition

In this work, we demonstrate dispersion engineering of silicon nitride waveguide resonators with atomic layer deposition (ALD). We conducted theoretical and experimental analyses on the waveguide dispersion with air cladding, hafnium oxide (HfO2) cladding, and aluminum oxide (Al2O3) cladding. By employing ALD HfO2 as the cladding layer, the dispersion of waveguide can be tuned to a finer degree in the normal regime at a wavelength of 1550 nm. On the other hand, using ALD Al2O3 cladding provides the waveguide dispersion that spans regimes in normal, near-zero, and anomalous dispersion.

Impact of process anneals on high-k/β-Ga2O3 interfaces and capacitance

Gallium oxide (β-Ga2O3) is becoming a popular material for high power electronic devices due to its wide bandgap and ease of processing. In this work, β-Ga2O3 substrates received various annealing treatments before atomic layer deposition of HfO2 and subsequent fabrication of metal–oxide–semiconductor (MOS) capacitors. Annealing of β-Ga2O3 with forming gas or nitrogen produced degraded capacitance–voltage (C–V) behavior compared to a β-Ga2O3 control sample with no annealing. A sample annealed with pure oxygen had improved C–V characteristics relative to the control sample, with a higher maximum capacitance and smaller flat-band voltage shift, indicating that oxygen annealing improved the C–V behavior. X-ray photoelectron spectroscopy also suggested a reduction in the oxygen vacancy concentration after O2 annealing at 450 °C, which supports the improved C–V characteristics and indicates that O2 annealing of β-Ga2O3 may lead to better MOS device performance.

Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO2.

The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO2 surface.

A theoretical study of the atomic layer deposition of HfO2 on Si(1 0 0) surfaces using tetrakis(ethylmethylamino) hafnium and water

The atomic layer deposition (ALD) of hafnium oxide (HfO2) thin film has attracted considerable attention owing to its crucial role in downscaling semiconductor devices. Herein, we theoretically investigated the reaction mechanisms during the ALD of HfO2 thin film (HfO2–ALD) on silicon (Si) surface using tetrakis(ethylmethylamino) hafnium (TEMAH) and water. By using two surface models, fully and partially hydroxylated Si(100) surfaces, we demonstrated that controlling the concentration of hydroxyl groups on the surface is important to enhance the activity for ligand-exchange reactions (LERs) of TEMAH and thereby effectively promote HfO2–ALD. During the precursor pulse, LERs on the fully hydroxylated Si(100) surface easily convert TEMAH into an unsaturated Hf atom with a low energy barrier of 25.8 kJ/mol, while mono(ethylmethylamino) hafnium (MEMAH) is obtained as the final product on the partially hydroxylated Si(100) surface with an energy barrier of 61.3 kJ/mol. The remaining ligand of the adsorbed MEMAH can be removed via LER with water during the water pulse. This work not only provides a better understanding of the conversion of TEMAH into a Hf atom on the hydroxylated Si(100) surface but also offers us more insights into the role of surface hydroxyls in the formation of HfO2 thin films.

Interfacial band parameters of ultrathin ALD–Al2O3, ALD–HfO2, and PEALD–AlN/ALD–Al2O3 on c-plane, Ga-face GaN through XPS measurements

Ultrathin oxides (UOs) and ultrathin nitrides (UNs) play a crucial role in forming lattice-mismatched semiconductor heterostructures that are fabricated by using semiconducting grafting approach. The grafting approach has shown its great potential to realize GaN-based heterojunction bipolar transistors by fulfilling the missing high-performance p-type nitrides with other p-type semiconductors. A handful of UO and UN dielectrics readily available by atomic layer deposition (ALD) satisfy the requirements of double-sided surface passivation and quantum tunneling for semiconductor grafting. Due to the states existing between the UO or UN conduction band and that of the GaN, the ALD deposited UO or UN layer can generate significant effects on the surface band-bending of GaN. Understanding the band parameters of the interface between UO or UN and c-plane Ga-face GaN can guide the selection of interfacial dielectrics for grafted GaN-based devices. In this study, we performed x-ray photoelectron spectroscopy measurements to obtain the band-bending properties on c-plane, Ga-face GaN samples coated by different ALD cycles of ultrathin-HfO2 or ultrathin AlN. The valence band spectra of GaN coated with ultrathin-ALD–Al2O3, ALD–HfO2, or PEALD–AlN/ALD–Al2O3 were further analyzed to calculate the valence and conduction band offsets between the ALD dielectrics and the Ga-face GaN under different thicknesses and post-deposition annealing conditions of the dielectrics.

ALD and PEALD deposition of HfO2 and its effects on the nature of oxygen vacancies

The high-k materials are essential in thin-film transistors. A well-controlled thin film deposition that produces less electronic defects induced by charged vacancies is highly desirable for avoiding high leakage current and and providing an exceptional dielectric strength. This work addresses the use of atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), and its variants to produce low-defective HfO2. The X-ray photoelectron spectroscopy (XPS) and Capacitance-Voltage (C-V) analysis revealed that the thermal ALD (TALD) samples produce electron emissions of ∼ 1 eV above the valence band maximum, negative flat band voltage shift of 1.51 V, and low dielectric breakdown strength (4.37 MV/cm). These properties confirm the high density of positive oxygen vacancies (1.2 × 1013 cm−2) acting as shallow traps, despite its O/Hf ratio (1.84) being higher than the Direct Plasma ALD (DPALD) sample. On the other hand, PEALD induces the formation of neutral vacancies promoted by the electric field of the plasma sheath. These defects are less detrimental to the capacitor performance as their flat band shifts are −0.25 and 1.01 V for remote plasma ALD (RPALD) and DPALD samples. Their dielectric breakdown strength increases by ∼ 1 MV/cm, and a reduced current density by 3 orders of magnitude less than TALD samples. The O/Hf ratio in DPALD samples is 1.80, confirming the benefits of using PEALD approaches.

Investigating the Efficacy of Hafnium Dioxide Barrier Layers to Halt Copper Oxide Formation in Redistribution Layers for Three-Dimensional (3D) Packaging

HfO2 is investigated for its suitability to act as an oxygen and moisture barrier to prevent Cu oxidation in redistribution layers (RDLs) in 3D packaging technologies. HfO2 barriers of varying thicknesses were deposited via atomic layer deposition (ALD) on Cu surfaces and then stressed by (i) high temperature stress and (ii) humidity and thermal stress for 1000 h to ascertain the optimal thickness to prevent oxidation of the Cu. The thickness of the ALD HfO2 film was monitored by ellipsometry, while the extent of Cu oxidation was monitored by focus ion beam prepared SEM cross sections. It is found that ∼9 nm of HfO2 is sufficient to prevent Cu oxidation.

Role of Temperature, Pressure, and Surface Oxygen Migration in the Initial Atomic Layer Deposition of HfO2on Anatase TiO2(101)

The atomic layer deposition of HfO2 on a TiO2(101) surface from tetrakis(dimethylamido)hafnium and water is investigated using a combination of in situ vacuum X-ray photoelectron spectroscopy (XPS) and time-resolved ambient pressure XPS. Precursor pressures and surface temperature are tuned as to map the space state of the deposition. In the initial stages of ALD, a reaction mechanism based on dissociative adsorption dominates over a classic ligand exchange mechanism, typically evoked when metal-amido complexes and water are used as the precursors for metal oxide ALD. Surface species, including a dimethyl ammonium ion and an imine, are identified. It is found that they can be formed only if the active role of the TiO2(101) surface is taken into consideration. The temperature of the surface enhances the formation of these species based on an insertion reaction of a hydrogen atom, which then assists the formation of more than the expected monolayer of HfO2. A HfO2 overlayer is produced already during the first half-cycle, enabled by a reduction of the TiO2 support. Dosing water at high pressure allows hydroxyl formation, which marks the transition toward a well-described ligand exchange reaction type. From the experiments performed, we find that the ALD of HfO2 at room temperature, performed at high pressure, is mainly based on dissociation and that no side reaction occurs. These insights into the ALD reaction mechanism highlight how in situ studies can help understand how deposition parameters affect the growth of HfO2 and how the ALD model for transition metal oxide formation from amido complexes and water can be extended.

Van der Waals epitaxy of 2D h-AlN on TMDs by atomic layer deposition at 250 °C

We report the demonstration of growing two-dimensional (2D) hexagonal-AlN (h-AlN) on transition metal dichalcogenide (TMD) monolayers (MoS2, WS2, and WSe2) via van der Waals epitaxy by atomic layer deposition (ALD). Having atomically thin thickness and high theoretical carrier mobility, TMDs are attractive semiconductors for future dense and high-performance 3D IC, and 2D hexagonal boron nitride (h-BN) as a gate dielectric is known to significantly improve TMD device performance. However, h-BN growth requires 1000 °C temperature that is not compatible with CMOS fabrication, and ALD deposition of any high-k 2D insulator on TMD continues to be an elusive goal. The epitaxial 2D layered h-AlN by low-temperature ALD is characterized by synchrotron-based grazing-incidence wide-angle x-ray scattering and high-resolution transmission electron microscopy. In addition, we demonstrate the feasibility of using layered h-AlN as an interfacial layer between WS2 and ALD HfO2. The significantly better uniformity and smoothness of HfO2 than that directly deposited on TMD are desirable characteristics for TMD transistor applications.

Plasma-Enhanced Atomic Layer Deposition of HfO2 with Substrate Biasing: Thin Films for High-Reflective Mirrors.

Tuning ion energies in plasma-enhanced atomic layer deposition (PEALD) processes enables fine control over the material properties of functional coatings. The growth, structural, mechanical, and optical properties of HfO2 thin films are presented in detail toward photonic applications. The influence of the film thickness and bias value on the properties of HfO2 thin films deposited at 100 °C using tetrakis(dimethylamino)hafnium (TDMAH) and oxygen plasma using substrate biasing is systematically analyzed. The HfO2 films deposited without a substrate bias show an amorphous microstructure with a low density, low refractive index, high incorporation of residual hydroxyl (OH) content, and high residual tensile stress. The material properties of HfO2 films significantly improved at a low bias voltage due to the interaction with oxygen ions accelerated to the film. Such HfO2 films have a higher density, higher refractive index, and lower residual OH incorporation than films without bias. The mechanical stress becomes compressive depending on the bias values. Further increasing the ion energies by applying a larger substrate bias results in a decrease of the film density, refractive index, and a higher residual OH incorporation as well as crystalline inclusions. The comparable material properties of the HfO2 films have been reported using tris(dimethylamino)cyclopentadienyl hafnium (TDMACpH) in a different apparatus, indicating that this approach can be transferred to various systems and is highly versatile. Finally, the substrate biasing technique has been introduced to deposit stress-compensated, crack- and delamination-free high-reflective (HR) mirrors at 355 and 532 nm wavelengths using HfO2 and SiO2 as high and low refractive index materials, respectively. Such mirrors could not be obtained without the substrate biasing during the deposition because of the high tensile stress of HfO2, leading to cracks in thick multilayer systems. An HR mirror for 532 nm wavelength shows a high reflectance of 99.93%, a residual transmittance of ∼530 ppm, and a low absorption of ∼11 ppm, as well as low scattering losses of ∼4 ppm, high laser-induced damage threshold, low mechanical stress, and high environmental stability.

Oxygen relocation during HfO2 ALD on InAs.

Atomic layer deposition (ALD) is one of the backbones for today's electronic device fabrication. A critical property of ALD is the layer-by-layer growth, which gives rise to the atomic-scale accuracy. However, the growth rate - or growth per cycle - can differ significantly depending on the type of system, molecules used, and several other experimental parameters. Typically, ALD growth rates are constant in subsequent ALD cycles, making ALD an outstanding deposition technique. However, contrary to this steady-state - when the ALD process can be entirely decoupled from the substrate on which the material is grown - the deposition's early stage does not appear to follow the same kinetics, chemistry, and growth rate. Instead, it is to a large extent determined by the surface composition of the substrate. Here, we present evidence of oxygen relocation from the substrate-based oxide, either the thermal or native oxide of InAs, to the overlayer of HfO2 in the initial ALD phase. This phenomenon enables control of the thickness of the initial ALD layer by controlling the surface conditions of the substrate prior to ALD. On the other hand, we observe a complete removal of the native oxide from InAs already during the first ALD half-cycle, even if the thickness of the oxide layer exceeds one monolayer, together with a self-limiting thickness of the ALD layer of a maximum of one monolayer of HfO2. These observations not only highlight several limitations of the widely used ligand exchange model, but they also give promise for a better control of the industrially important self-cleaning effect of III-V semiconductors, which is crucial for future generation high-speed MOS.