Advanced Atomic Layer Deposition Research Articles

(Invited) Low Temperature Atomic Layer Deposition Processes for Large-Area Synthesis of 2D Transition Metal Dichalcogenides

2D materials have been the focus of intense research in the last decade due to their unique physical properties. This presentation will highlight our recent progress on the large-area synthesis of two-dimensional transition metal chalcogenides for nanoelectronics using advanced atomic layer deposition cycle schemes. First, how we can use advanced cycle schemes to deposit wafer-scale polycrystalline MoS2 thin films at very low temperatures down to 100 °C. We have identified the critical role of hydrogen during the plasma step in controlling the composition and properties of molybdenum sulfide films. By increasing the H2/H2S ratio or adding an extra hydrogen plasma step to our ALD process, we are able to deposit pure polycrystalline MoS2 films at temperatures as low as 100 °C. To the best of our knowledge, this represents the lowest temperature for crystalline MoS2 films prepared by any chemical gas-phase method.[1]The most dominant methods for preparing MoS2 via ALD is to alternately expose a substrate to a metalorganic precursor and a hydrogen sulfide (H2S) or a plasma containing H2S. H2S is a corrosive, toxic, and flammable gas that is heavier than air, which makes it hazardous and expensive to store, install, and transport. Alternative sulfur precursors in the solid or liquid phase would be beneficial in terms of cost and safety and would require the installation of no additional hardware for most ALD reactors. In the second half of this contribution, the widely researched ALD process using bis(tert-butylimido)bis(dimethylamino)molybdenum(IV) ((tBuN)2(NMe2)2Mo) and H2S plasma is compared to a novel ALD process using (tBuN)2(NMe2)2Mo, hydrogen plasma, and di-tert-butyl disulfide (TBDS), which is an inexpensive, liquid-phase sulfur precursor.[1] M. Mattinen et al., Chem. Mater. (2022), 34, 5104

(Invited) Advanced Atomic Layer Deposition Cycle Schemes for Large-Area Synthesis of 2D Transition Metal Dichalcogenides

2D materials have been the focus of intense research in the last decade due to their unique physical properties. This presentation will highlight our recent progress on the large-area synthesis of two-dimensional transition metal chalcogenides for nanoelectronics using advanced atomic layer deposition cycle schemes. First, how we can use advanced cycle schemes to deposit wafer-scale polycrystalline MoS2 thin films at very low temperatures down to 100 °C. We have identified the critical role of hydrogen during the plasma step in controlling the composition and properties of molybdenum sulfide films. By increasing the H2/H2S ratio or adding an extra hydrogen plasma step to our ALD process, we are able to deposit pure polycrystalline MoS2 films at temperatures as low as 100 °C. To the best of our knowledge, this represents the lowest temperature for crystalline MoS2 films prepared by any chemical gas-phase method.[1]ALD-grown 2D films tend to exhibit a high density of out-of-plane 3D structures in addition to 2D horizontal layers. While the out-of-plane 3D structures are ideal for catalysis applications, the presence of such 3D structures can hinder charge transport, which hampers device applications. In this presentation I will show how we used mechanistic insight obtained by HRTEM to tune the shape and density of the 3D structures during plasma-enhanced ALD using advanced atomic layer deposition schems. The obtained morphology control was further confirmed by electrical measurements.[2]Earlier [3] we have shown that ALD is an excellent technique to make MoxW1-xS2 alloys with precise control over the alloy composition. Here, I will focus on how (plasma-enhanced) atomic layer deposition can aid in synthesizing doped 2DTMCs with precise control over the doping concentration by using elaborate ALD dosing schemes.[1] M. Mattinen et al., Chem. Mater. (2022), 34, 5104[2] S. Balasubramanyam, et al. ACS Appl. Mater. Interfaces (2020), 12, 3873[3] J. J. P. M. Schulpen et al. 2D Mater. (2022), 9, 025016

Toolbox of Advanced Atomic Layer Deposition Processes for Tailoring Large-Area MoS2 Thin Films at 150 °C.

Two-dimensional MoS2 is a promising material for applications, including electronics and electrocatalysis. However, scalable methods capable of depositing MoS2 at low temperatures are scarce. Herein, we present a toolbox of advanced plasma-enhanced atomic layer deposition (ALD) processes, producing wafer-scale polycrystalline MoS2 films of accurately controlled thickness. Our ALD processes are based on two individually controlled plasma exposures, one optimized for deposition and the other for modification. In this way, film properties can be tailored toward different applications at a very low deposition temperature of 150 °C. For the modification step, either H2 or Ar plasma can be used to combat excess sulfur incorporation and crystallize the films. Using H2 plasma, a higher degree of crystallinity compared with other reported low-temperature processes is achieved. Applying H2 plasma steps periodically instead of every ALD cycle allows for control of the morphology and enables deposition of smooth, polycrystalline MoS2 films. Using an Ar plasma instead, more disordered MoS2 films are deposited, which show promise for the electrochemical hydrogen evolution reaction. For electronics, our processes enable control of the carrier density from 6 × 1016 to 2 × 1021 cm-3 with Hall mobilities up to 0.3 cm2 V-1 s-1. The process toolbox forms a basis for rational design of low-temperature transition metal dichalcogenide deposition processes compatible with a range of substrates and applications.

Highly dispersed Fe-decorated Ni nanoparticles prepared by atomic layer deposition for dry reforming of methane

Dry reforming of methane (DRM) is a sustainable chemical process that can simultaneously transform methane and carbon dioxide, which are generally considered greenhouse gases, into syngas with H2/CO ratio close to 1. The deposition of carbon on the active sites during long-period DRM tests will lead to severe deactivation of Ni-based catalysts. Thus, in this work, we proposed a series of uniformly dispersed Fe-decorated Ni/Al2O3 catalysts via atomic layer deposition (ALD) to solve this key issue. Modification with trace amounts of Fe (0.3–0.6%) had multiple effects on facilitating the CH4 dissociation on Ni0, improving the low-temperature catalytic activity, moderating the carbon species and accelerating coke oxidation. The sample denoted as 0.3%Fe/Ni/Al2O3 exhibited almost no activity loss in the 72 h test at 650 °C. The Fe-decorated Ni/Al2O3 structure achieved a balance between the enhancement of CH4 cracking and the elimination of coke. Furthermore, this advanced ALD approach of preparing uniform secondary metal nanoparticle-decorated catalysts provided guidance to other bimetallic systems, such as Pt/Ni, Mn/Ni, and Cu/Ni.

Super-conformal TiN thin film deposition by carrier pulse purge atomic layer deposition system: Chamber design optimization with computational fluid dynamics

Owing to the increase in demand for the shrinkage of semiconductor design rules and the advent of the three-dimensional structure of semiconductor devices, atomic layer deposition (ALD) has emerged as an attractive alternative to conventional chemical vapor deposition techniques. Although the development of precursors and characterization of ALD films have been widely studied, few studies have been conducted on the modification of ALD parameters and optimization of the ALD process. In this study, an advanced ALD titanium nitride (TiN) system was designed using a pumping and purging simulationBased on the simulation results, we adopted a carrier pulse purge method, where TiCl4 fed, purge N2, pulse purge N2, purge N2, NH3 fed, purge N2, pulse purge N2, and purge N2 were alternatively injected into the chamber in the ALD cycle. Compared to the conventional purge method, the carrier pulse purge method can reduce the ALD cycle time by 18.27% and yields a high-quality (high step coverage, 98 %) TiN film with lower electrical resistivity and chlorine impurity. This carrier pulse purge method can ultimately lead to improved throughput and productivity in the semiconductor industry by reducing the ALD cycle time.

Advanced atomic layer deposition (ALD): controlling the reaction kinetics and nucleation of metal thin films using electric-potential-assisted ALD

Electric-potential-assisted atomic layer deposition was demonstrated for Ru film growth. Surface reaction was modified via the electric potential, which affected the nucleation and microstructure of films. Assorted film properties were improved notably.

Magneto-Optical and Muliferroic Properties of Transition-Metal (Fe, Co, or Ni)-Doped ZnO Layers Deposited by ALD.

ZnO doped with transition metals (Co, Fe, or Ni) that have non-compensated electron spins attracts particular interest as it can induce various magnetic phenomena and behaviors. The advanced atomic layer deposition (ALD) technique makes it possible to obtain very thin layers of doped ZnO with controllable thicknesses and compositions that are compatible with the main microelectronic technologies, which further boosts the interest. The present study provides an extended analysis of the magneto-optical MO Kerr effect and the dielectric properties of (Co, Fe, or Ni)-doped ZnO films prepared by ALD. The structural, magneto-optical, and dielectric properties were considered in relation to the technological details of the ALD process and the corresponding dopant effects. All doped samples show a strong MO Kerr behavior with a substantial magnetization response and very high values of the Kerr polarization angle, especially in the case of ZnO/Fe. In addition, the results give evidence that Fe-doped ZnO also demonstrates a ferroelectric behavior. In this context, the observed rich and versatile physical nature and functionality open up new prospects for the application of these nanostructured materials in advanced electronic, spintronic, and optical devices.

Advanced Atomic Layer Deposition: Ultrathin and Continuous Metal Thin Film Growth and Work Function Control Using the Discrete Feeding Method.

The ultrathin and continuous ruthenium (Ru) film was deposited through an improved atomic layer deposition (ALD) process with a discrete feeding method (DFM), called DF-ALD, employing a cut-in purge step during the precursor feeding. The excess precursor molecules can be physically adsorbed onto the chemisorbed precursors on the substrate during precursor feeding, which screens the reactive sites on the surface. Using DF-ALD, surface coverage of precursors was enhanced because the cut-in purge removes the physisorbed precursors securing the reactive sites beneath them; thus, nucleation density was greatly increased. Therefore, the grain size decreased, which changed the microstructure and increased oxygen impurity concentration. However, a more metallic Ru thin film was formed due to thermodynamic stability and improved physical density. Consequently, DF-ALD enables the deposition of the ultrathin (3 nm) and continuous Ru film with a low resistivity of ∼60 μΩ cm and a high effective work function of ∼4.8 eV.

Efficient Modulation of Electrocatalyst Interfaces by Atomic Layer Deposition: Fundamentals to Application

Under the scope of “carbon neutrality” and “emissions peak,” renewable energy technologies and systems relying on electrocatalytic reactions (e.g., oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and carbon dioxide reduction reaction (CO2RR)), though kinetically slow, are attractive. To promote the efficiency of such systems, engineering of the electrocatalyst interface is an effective strategy. In the fabrication toolbox for complex surface/interface, the advanced atomic‐layer deposition (ALD) technique is superior to conventional methods, evidenced by precise control of thickness, composition, uniformity, etc. This review summarizes recent developments in ALD implementation in a variety of electrocatalytic systems, especially the electrode interface preparation and modulation. Beyond all doubt, the introduction of the ALD process could dramatically increase the number of electrocatalytic‐active sites and hence improve the performance. However, its practical application in this field is open to deliberation, while process cost and complexity are in consideration.

Relation between Reactive Surface Sites and Precursor Choice for Area-Selective Atomic Layer Deposition Using Small Molecule Inhibitors.

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.

(Invited) Advanced ALD Applications

CMOS device feature size down-scaling is still continuous. Nowadays it reaches 5nm and beyond. The technology development in semiconductor industry encounters many new challenges. As consequences, new materials and new techniques are required to meet the challenges.At 45nm technology node, Atomic Layer Deposition (ALD) is introduced for gate stack process. Since then ALD is being used more and more in advanced technology nodes because of its intrinsic process features, e.g. accurate thickness control and excellent step coverage etc. Especially for the reduced feature sizes, ALD exhibits as a powerful technique, not only in gate stack, but also in advanced patterning process (SADP and SAQP) and advanced metallization barrier materials etc.Hf-based hik material deposited by ALD is widely used in logic gate stack and memory capacitor. Recently Hf-based materials are continuously getting more attentions due to its intrinsic features. It is reported that Hf-based materials can exhibit different resistor stage. Therefore it can be used as memristor in ReRAM. People also report Hf-based materials can be crystalized into orthorhombic phase and thus exhibit ferroelectric characteristics[1,3]. Based on this feature, it can be used in NCFET and FeRAM. In this paper, we can going to review the applications of Hf-based materials deposited by ALD in new memory fields.Although device down-scaling is still going on, the challenges are tremendous. As an alternative, 3D-IC packaging, stacks different chip together and increases the packaging density and chip performance. Therefore, recently 3D-IC packaging is getting more and more attractive. However, there are many constrains in 3D-IC packaging, e.g. low thermal budget, high aspect ratio structure, excellent film quality etc.. ALD is gradually accepted in 3D-IC packaging due to its intrinsic features. In this paper, we are going to discuss some ALD applications in advanced 3D-IC packaging.REFERENCES[1] J. Müller et al, NanoLetters, vol. 12, no. 8, pp. 4318-4323, 2012.[2] M. H. Lee et al, IEEE J. of the Electron Device Society, vol. 3, no. 4, pp. 377-381, 2015.[3] M. H. Lee et al, IEEE Electron Device Letter, vol. 36, no. 4, pp. 294-296, 2015.

Encapsulation of Co3 O4 Nanocone Arrays via Ultrathin NiO for Superior Performance Asymmetric Supercapacitors.

Designing of multicomponent transition metal oxide system through the employment of advanced atomic layer deposition (ALD) technique over nanostructures obtained from wet chemical process is a novel approach to construct rational supercapacitor electrodes. Following the strategy, core-shell type NiO/Co3 O4 nanocone array structures are architectured over Ni-foam (NF) substrate. The high-aspect-ratio Co3 O4 nanocones are hydrothermally grown over NF following the precision controlled deposition of shell NiO considering Co3 O4 nanocone as host. NiO thickness of 5 nm exhibits the highest specific capacity of 1242 C g-1 (2760 F g-1 ) at current density 2 A g-1 , which is greater than pristine Co3 O4 @NF (1045.8 C g-1 or 2324 F g-1 ). The rate capability with 5 nm NiO/Co3 O4 @NF nanocone structures is about 77% whereas Co3 O4 @NF retains 46 % of capability at 10 A g-1 . The ultrathin ALD 5 nm NiO accelerates both rate capability and 95.5% cyclic stability after 12 000 charge-discharge cycles. An asymmetric device fabricated between 5 nm NiO/Co3 O4 @NF (positive) || activated carbon (negative) achieves an energy density of 81.45 Wh kg-1 (4268 W kg-1 ) with good cycling device stability. Additionally, LEDs can be energized by two ASC device in series. This work opens the path in both advanced electrode material and surface modification of earth-abundant systems for efficient and real-time supercapacitor applications.

Variation of shell thickness in ZnO-SnO2 core-shell nanowires for optimizing sensing behaviors to CO, C6H6, and C7H8 gases

ZnO-SnO2 core-shell nanowires (C-S NWs) with different shell thicknesses (0–120 nm) were prepared and their sensing behavior was systematically studied. ZnO-SnO2 C-S NWs were prepared using a two-step synthesis procedure, where core ZnO NWs were synthesized by a vapor-liquid-solid growth technique, and subsequently these cores were coated with SnO2 shell layers by using an advanced atomic layer deposition technique. The sensors were exposed to 10-ppm CO, C6H6, and C7H8 gases at an optimal working temperature. The shell thickness was optimized to be 40 nm, for which the sensor revealed the highest sensitivity and fastest dynamics to the above-mentioned gases. The sensing mechanism was discussed in detail and the dominant mechanism was related to the radial modulation effect as well as the volume fraction of the shell to the total volume of C-S NWs.

(Invited) Atomic Layer Deposition Coatings for Medical Devices

Implantable medical devices must withstand the corrosive environment inside the human body for prolonged periods of time. Hermetic sealing of the device to protect it from the corrosive environment of human body and vice versa is a key step to enable long life time for the smart medical devices. Atomic layer deposition (ALD) is an advanced deposition technique belonging to the family of chemical vapor deposition (CVD) techniques. In ALD the substrate to be coated is exposed sequentially to precursor chemicals that react with the reactive surface sites on the substrate and form a chemically bonded adsorption layer. This growth mode of the film enables extremely conformal and uniform films to be coated on three-dimensional objects having any shape. Even the smallest, nanometer sized features on the objects can be coated with ease, making the technique extremely useful when hermetic sealing of complex shaped objects are required. The advantages of ALD over other deposition techniques makes it powerful method for applications where sensitive substrate materials combine with extreme demands on coating quality and temperature/chemical resistance, such as those often seen in the medical applications. In order to make a robust protective sealing for the medical device, the film properties must fulfill certain key criteria. First and foremost, the film material needs to be non-toxic for human cells in order to be biocompatible. Secondly, the film needs to function as an highly efficient diffusion barrier against the ions and molecules present in body fluids. In addition, the adhesion of the film with the device surface needs to be strong enough to prevent the delamination of the film. In our recent work [1] we have shown that SiO2-HfO2 coated sub-millimeter-sized microelectronic chiplets for wireless body implants can last without degradation and electronic failure in accelerated aging tests in saline at T = 87 °C for more than 180 days. This corresponds an equivalent lifetime of more than 10 years at human body equivalent temperature of 37 °C. Latest results on ALD films (deposited with Picosun® R-200 Advanced ALD reactor) for medical applications will also be discussed. Biocompatibility tests for Al2O3, TiO2, HfO2, SiO2, Ta2O5 films using the ISO standard Cytotoxicity of Medical Device (ISO 10993-5) procedure will be presented. In addition, we will show results of corrosion tests in PBS solution at elevated temperature (87 °C) for a number of ALD oxides and their nanolaminates, highlighting a stress control method that can improve the long-term delamination resistance of the coatings. Furthermore, we will show some results on the diffusion barrier properties of Al2O3, TiO2, HfO2, SiO2, Ta2O5 and their nanolaminates on different electrode materials (Al, Au, Pt, TiN) when exposed to PBS solution. [1] Conformal Hermetic Sealing of Wireless Microelectronic Implantable Chiplets by Multilayered Atomic Layer Deposition (ALD) by J. Jeong, F. Laiwalla, J. Lee, R. Ritasalo, M. Pudas, L. Larson, V. Leung, and A. Nurmikko, https://doi.org/10.1002/adfm.201806440. Acknowledgements: This work is part of the ULIMPIA project funded by PENTA under grant number PENTA-2017-Call2-16101-ULIMPIA

Recent Progresses and Development of Advanced Atomic Layer Deposition towards High-Performance Li-Ion Batteries.

Electrode materials and electrolytes play a vital role in device-level performance of rechargeable Li-ion batteries (LIBs). However, electrode structure/component degeneration and electrode-electrolyte sur-/interface evolution are identified as the most crucial obstacles in practical applications. Thanks to its congenital advantages, atomic layer deposition (ALD) methodology has attracted enormous attention in advanced LIBs. This review mainly focuses upon the up-to-date progress and development of the ALD in high-performance LIBs. The significant roles of the ALD in rational design and fabrication of multi-dimensional nanostructured electrode materials, and finely tailoring electrode-electrolyte sur-/interfaces are comprehensively highlighted. Furthermore, we clearly envision that this contribution will motivate more extensive and insightful studies in the ALD to considerably improve Li-storage behaviors. Future trends and prospects to further develop advanced ALD nanotechnology in next-generation LIBs were also presented.

Promising Applications of Advanced Atomic Layer Deposition in Lithium Ion Batteries

not Available.

Quantitative analysis on the influences of the precursor and annealing temperature on Nd2O3 film composition

In this paper, ultra-thin Nd2O3 dielectric films are deposited on p-type silicon substrates by advanced atomic layer deposition method. Nd (thd)3 and O3 are used as the reaction precursors separately. The as-grown samples are annealed in N2 atmosphere in a temperature range of 700900 ℃. The samples are investigated at room temperature by X-ray photoelectron spectroscopy and the changes of the film composition at different annealing temperatures are discussed in detail. For a higher precursor temperature of 185 ℃ in the deposition process, the ratio of oxygen to neodymium atoms for the as-grown film is 1.82, which is close to the stoichiometry. Dielectric constant increases from 6.85 to 10.32.

Charge trapping memory devices employing multi-layered Ge/Si nanocrystals for storage fabricated with ALD and PLD methods

The Ge/Si nanocrystals on ultra thin high-k tunnel oxide Al2O3 were fabricated to form the charge trapping memory prototype with asymmetric tunnel barriers through combining the advanced atomic layer deposition (ALD) and pulse laser deposition (PLD) techniques. Charge storage characteristics in such memory structure have been investigated using capacitance-voltage (C-V) and capacitance-time (C-t) measurements. The results prove that both the two-layered and three-layered memory structures behave relatively qualified for the multi-level cell storage. The results also demonstrate that compared to electrons, holes reach a longer retention time even with an ultra thin tunnel oxide owing to the high band offset at the valence band between Ge and Si.

Design and Development of ALD Precursors for Microelectronics

Atomic Layer Deposition (ALD) has been identified as one of the primary technologies to fabricate devices with novel architecture. This requires design and development of advanced ALD precursors that can withstand the rigors of various integration steps while delivering the high quality layers essential to the new device design. The design criteria require these precursors to have suitable thermal stability, volatility, purity, reactivity, scalability, and economic viability. This brief review describes various elements of a precursor screening/development cycle from the materials company perspective. Specific examples will be presented for precursors of selected metals (such as ruthenium and cobalt) and high-k dielectrics (Hf, Zr, Ln) oxide materials.

Application of Advanced Atomic Layer Deposition for Understanding and Control of VTH and EOT in Metal/High-k Gate Stacks

This paper discusses applications of atomic layer deposition (ALD) for both understanding and control of various challenges in metal/high-k gate stacks for advanced CMOS. Though ALD is generally used for high-k film deposition, this work focuses on understanding and controlling both anomalous VTH behaviors observed in high-k gate stacks and EOT scalability down to 0.5 nm.