AVS 70 Session AP2+EM+PS+TF-WeM: New Advances in Atomic Layer Deposition

As the microelectronics sector advances towards further miniaturization, precision in thin film deposition becomes crucial. Traditional Atomic Layer Deposition (ALD) techniques, vital for semiconductor manufacturing, often require extensive surface preparation, limiting throughput. ATLANT 3D's µDALP™ technology adapts ALD using microreactor technology for localized thin film deposition with accuracy down to a few hundred microns, maintaining all conventional ALD benefits. This approach uses micronozzles for precise delivery of precursors, allowing rapid film formation on targeted substrate areas under atmospheric conditions. The µDALP™ achieves a vertical resolution of 0.2 nm, offering exceptional precision.

This technology enhances conventional ALD's capabilities in selective patterning for microfluidic channels, optical gratings, and nanostructured surfaces, improving its use in next-generation device fabrication. This presentation will discuss how µDALP™ retains ALD's core advantages while enhancing scalability, processing speed, and cost-efficiency. We will highlight the transformative impact of µDALP™ on thin-film manufacturing across optics, photonics, MEMS, and advanced electronics, underscoring its potential to propel future innovations in energy storage and conversion, quantum computing, and advanced packaging solutions.

Keywords:Atomic Layer Deposition, µDALP™, Nanotechnology, Thin Film, Microelectronics.

Fig. 1. (a)Top view of aligned Si trenches (aligned horizontally) coated with a perpendicular line of TiO2(low magnification SEM). (b) Microfluidic precursor delivery concept: Schematic view of the delivery nozzle in frontal view (top) and in cross-section (lower panel).

References

​​(1)Parsons, G. N.; Clark, R. D.,2020, 32(12), 4920–4953.

​(3)Kundrata, I.; Barr, M. K. S.; Tymek, S.; Döhler, D.; Hudec, B.; Brüner, P.; Vanko, G.; Precner, M.; Yokosawa, T.; Spiecker, E.,Small Methods2022, 6(5), 2101546.​

Membranes with tunable, sub-nanometer pores are needed for molecular separations in applications including water treatment, critical mineral extraction, and recycling.Ceramic membranes are a promising alternative to the polymeric membranes typically used in such applications due to their robust operation under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. In this presentation, we describe a ceramic thin film composite (TFC) membrane fabrication method that achieves sub-nm pore size control using atomic layer deposition (ALD) by incorporating a molecular-scale porogen.By co-dosing alkyl alcohols along with the H₂O coreactant during Al₂O₃ ALD, we incorporate alkoxide species in the film which create a continuous network of pores upon calcination.Varying the alkyl alcohol (methanol, ethanol, isopropanol) tunes the pore size.We use Fourier transform infrared absorption spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy to elucidate the surface chemistry and growth during the alcohol-modulated ALD as well as the subsequent pore formation.We evaluate the transport and separations properties of the ALD TFC membranes using a two-chamber diffusion cell with aqueous salt solutions.We measured a remarkable enhancement in the transport of Cl^- compared to SO₄^2- (8.6 times faster) matching the selectivity of state-of-the-art polymer membranes.We attribute this selectivity to the dehydration of the large divalent ions within the subnanometer pores. In addition, permeation studies using neutral adsorbates revealed average pore sizes of ~7Å, 13Å, and 19Å for ALD TFC membranes prepared using methanol, ethanol, and isopropanol, respectively.This work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using ALD.

Over the past 20+ years, a wide variety of nanocomposite thin films with unique property combinations have been produced by atomic layer deposition (ALD) infiltration of nanoparticle (NP) films. Examples include electrochromic WO_{3 – x} NP films with photochemical stability enhanced by Ta₂O₅ ALD¹ and superhydrophilic and antireflective TiO₂/SiO₂ NP films with elastic modulus and hardness enhanced by Al₂O₃ ALD.² Applications of such nanocomposite films, however, are limited by their small thickness (typically a few μm or thinner), reliance on substrates, and/or residual porosity that can remain after ALD infiltration.

In this work, we explore fabrication of macroscopic, freestanding, dense nanocomposites—pucks with ~1 mm thickness, ~10 mm diameter, and solid volume fraction that can exceed 99%—via ALD infiltration of NP compacts followed by pressure-assisted sintering. For a prototype, we use monodisperse 100 nm SiO₂ NPs and an ALD coating of Al-doped ZnO to form electrically conductive ceramic nanocomposites with electrical and optical properties dependent on the coating thickness. Infiltration of the ultra-high-aspect-ratio (>10,000) SiO₂ NP compacts with ZnO:Al is accomplished via a recently developed cyclical-temperature ALD process.³ The ZnO:Al-coated SiO₂ compacts are then densified via environmentally controlled pressure-assisted sintering (EC-PAS), wherein NPs are cleaned and kept in an inert atmosphere to maintain high surface energy, which enables low-temperature densification with minimal grain growth.⁴ An EC-PAS process with a maximum pressure of ~2 GPa and a maximum temperature of 450 °C yields dense SiO₂/ZnO:Al nanocomposites that contain nanocrystalline ZnO:Al networks and exhibit low electrical resistivity, ρ. At nominal ZnO:Al coating thicknesses, t, of ~3 nm and ~6 nm, ρ is on the order of 1 and 0.1 Ω-cm, respectively, at 300 K. Moreover, at t ≈ 6 nm, the Hall mobility approaches 1 cm²V^-1s^-1 at 300 K, and ρ increases by less than a factor of 3 upon cooling to 10 K, suggesting proximity to the metallic/band-like charge transport regime. Interestingly, the nanocomposites are blue in color with transparency and hue apparently dependent on t. Characterization techniques employed in our investigation into these electrical and optical properties include X-ray diffractometry, scanning electron microscopy, Hall and Seebeck effect measurements, absorption/transmission/reflection spectroscopy, and photoluminescence spectroscopy and imaging.

1. Y. Wang et al., Chem. Mater. 28, 7198 (2016)
2. M. I. Dafinone et al., ACS Nano 5, 5078 (2011)
3. B. L. Greenberg et al., J. Vac. Sci. Technol. A 42, 012402 (2024)
4. H. Ryou et al., ACS Nano 12, 3083 (2018)

Far-ultraviolet (FUV) astronomy (λ = 100-200 nm) relies on efficient Al mirrors because Al has a very high theoretical reflectance in this region. However, since Al readily oxidizes in air, the strongly absorbing native oxide layer appreciably degrades its FUV performance. A novel surface passivation technique for Al mirrors was previously demonstrated using an electron beam (e-beam) generated SF₆/Ar plasma, which proceeds via a combined etching of the native oxide and simultaneous fluorination of the Al surface [1].

In our present work, this novel e-beam plasma technique is integrated into a plasma-enhanced atomic layer deposition (PEALD) system. We use a Veeco Fiji G2 reactor, equipped with substrate biasing, that has been uniquely modified to include an on-axis e-beam generated plasma source. Trimethylaluminum (TMA) and SF₆/Ar plasma, produced with an inductively coupled plasma (ICP) source, were used as our precursor and reactant for the ALD AlF₃ process. Optimization of the ALD parameters was performed, and our best ALD AlF₃ films (F/Al ≈ 3, ~1% oxygen content, and roughness < 1 nm) were attained using 100 W ICP power and total plasma gas flows > 30 sccm. Our ALD AlF₃ films provide improved FUV reflectivity compared to oxidized bare Al, however, these optical properties are still limited by Al oxide at the AlF₃/Al interface. To overcome this, we utilize our in-situ e-beam plasma, produced in a gas mixture of SF₆/Ar, to minimize the native oxide layer prior to ALD.

In this talk, we discuss the processing parameters of the in-situ e-beam plasma (SF₆/Ar ratio and flow, sample bias) and how they affect the AlF₃ growth rate, film/interface chemistry, and surface roughness. These material properties are related to optical performance, which compares favorably to state-of-the-art coatings (≈90% at 121 nm). We then discuss hybrid AlF₃ films, in which the growth is initiated by e-beam plasma, and then continued using an optimized ALD AlF₃ recipe. For the initial step, pre-treatments using the in-situ e-beam plasma and the previously developed ex-situ e-beam plasma [1] are compared. We show that both in-situ and ex-situ hybrid techniques significantly reduce the interfacial oxygen compared to ALD AlF₃ alone (no pre-treatment), which enhances the FUV reflectivity. This work highlights the importance of the interface quality of passivated Al mirrors on their optical performance in the FUV range.

This work is supported by NASA Astrophysical Research and Analysis (APRA) grant 20-APRA20-0093/ N0017322GTC0044 and is partially supported by the NRL Base program through the Office of Naval Research.