For continual scaling in microelectronics, new processes for precise high volume fabrication are required. Area-selective atomic layer deposition (ASALD) can provide an avenue for self-aligned material patterning and offers an approach to correct edge placement errors commonly found in top-down patterning processes. Two-dimensional transition metal dichalcogenides also offer great potential in scaled microelectronic devices due to their high mobilities and few-atom thickness. In this work, we report ASALD of MoS2 thin films by deposition with MoF6 and H2S precursor reactants. The inherent selectivity of the MoS2 atomic layer deposition (ALD) process is demonstrated by growth on common dielectric materials in contrast to thermal oxide/ nitride substrates. The selective deposition produced few layer MoS2 films on patterned growth regions as measured by Raman spectroscopy and time-of-flight secondary ion mass spectrometry. We additionally demonstrate that the selectivity can be enhanced by implementing atomic layer etching (ALE) steps at regular intervals during MoS2 growth. This area-selective ALD process provides an approach for integrating 2D films into next-generation devices by leveraging the inherent differences in surface chemistries and providing insight into the effectiveness of a supercycle ALD and ALE process.
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Area‐selective atomic layer deposition on HOPG enabled by writable electron beam functionalization
Area‐selective atomic layer deposition (AS‐ALD) techniques are an emerging class of bottom‐up nanofabrication techniques that selectively deposit patterned ALD films without the need for conventional top‐down lithography. To achieve this patterning, most reported AS‐ALD techniques use a chemical inhibitor layer to proactively block ALD surface reactions in selected areas. Herein, an AS‐ALD process is demonstrated that uses a focused electron beam (e‐beam) to dissociate ambient water vapor and “write” highly resolved hydroxylated patterns on the surface of highly oriented pyrolytic graphite (HOPG). The patterned hydroxylated regions then support subsequent ALD deposition. The e‐beam functionalization technique facilitates precise pattern placement through control of beam position, dwell time, and current. Spatial resolution of the technique exceeded 42 nm, with a surface selectivity of between 69.9% and 99.7%, depending on selection of background nucleation regions. This work provides a fabrication route for AS‐ALD on graphitic substrates suitable for fabrication of graphene‐based nanoelectronics.
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- Award ID(s):
- 1651538
- NSF-PAR ID:
- 10470829
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Nano Select
- Volume:
- 3
- Issue:
- 10
- ISSN:
- 2688-4011
- Page Range / eLocation ID:
- 1448 to 1457
- Subject(s) / Keyword(s):
- ["area-selective atomic layer deposition, alumina, electron beam, hydroxl"]
- Format(s):
- Medium: X Other: pdf
- Sponsoring Org:
- National Science Foundation
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Modern-day chip manufacturing requires precision in placing chip materials on complex and patterned structures. Area-selective atomic layer deposition (AS-ALD) is a self-aligned manufacturing technique with high precision and control, which offers cost effectiveness compared to the traditional patterning techniques. Self-assembled monolayers (SAMs) have been explored as an avenue for realizing AS-ALD, wherein surface-active sites are modified in a specific pattern via SAMs that are inert to metal deposition, enabling ALD nucleation on the substrate selectively. However, key limitations have limited the potential of AS-ALD as a patterning method. The choice of molecules for ALD blocking SAMs is sparse; furthermore, deficiency in the proper understanding of the SAM chemistry and its changes upon metal layer deposition further adds to the challenges. In this work, we have addressed the above challenges by using nanoscale infrared spectroscopy to investigate the potential of stearic acid (SA) as an ALD inhibiting SAM. We show that SA monolayers on Co and Cu substrates can inhibit ZnO ALD growth on par with other commonly used SAMs, which demonstrates its viability towards AS-ALD. We complement these measurements with AFM-IR, which is a surface-sensitive spatially resolved technique, to obtain spectral insights into the ALD-treated SAMs. The significant insight obtained from AFM-IR is that SA SAMs do not desorb or degrade with ALD, but rather undergo a change in substrate coordination modes, which can affect ALD growth on substrates.
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Patterned deposition and 3D fabrication techniques have enabled the use of hydrogels for a number of applications including microfluidics, sensors, separations, and tissue engineering in which form fits function. Devices such as reconfigurable microvalves or implantable tissues have been created using lithography or casting techniques. Here, we present a novel open-microfluidic patterning method that utilizes surface tension forces to form hydrogel layers on top of each other, into a patterned 3D structure. We use a patterning device to form a temporary open microfluidic channel on an existing gel layer, allowing the controlled flow of unpolymerized gel in device-regions. After layer gelation and device removal, the process can be repeated iteratively to create multi-layered 3D structures. The use of open-microfluidic and surface tension-based methods to define the shape of each individual layer enables patterning to be performed with a simple pipette and with minimal dead-volume. Our method is compatible with unmodified (native) biological hydrogels, and other non-biological materials with precursor fluid properties compatible with capillary flow. With our open-microfluidic layer-by-layer fabrication method, we demonstrate the capability to build agarose, type I collagen, and polymer–peptide 3D structures featuring asymmetric designs, multiple components, overhanging features, and cell-laden regions.more » « less
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Abstract Area‐selective deposition (ASD) is a forefront nanopatterning technique gaining substantial attention in the semiconductor industry. While current research primarily addresses single‐material ASD, exploring multi‐material ASD is essential for mitigating complexity in advanced nanopatterning. This study describes molybdenum hexafluoride (MoF6)‐mediated fluorination/passivation of the hydroxylated SiO2(SiO2‒OH) at 250 °C as a new method to pacify nucleation during subsequent ZnO and TiO2atomic layer deposition (ALD). In contrast, Al2O3ALD is not passivated on the fluorinated SiO2(SiO2‒F). The study further shows that Mo ALD using MoF6and silane (1 wt% SiH4in Ar) selectively proceeds on hydrogen‐terminated Si (Si‒H), whereas SiO2‒OH becomes fluorine‐passivated without observable Mo deposition. This enables subsequent ZnO and TiO2ASD on Mo versus SiO2‒F, as confirmed by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). Proposed growth and inhibition mechanisms highlight the importance of the metal oxide precursor in achieving selectivity. Taken together, self‐aligned Mo/ZnO and Mo/TiO2nanoribbons are demonstrated on coplanar nanoscale Si‒H/SiO2‒OH patterns by sequentially integrating two individual ASD processes: 1) Mo ASD on Si‒H versus SiO2‒OH; and 2) ZnO or TiO2ASD on Mo versus SiO2‒F. This work highlights the potential for this approach in new ASD systems.
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Abstract From its inception, extensive work on the characterization of field effect transistors (FETs) based on 2D‐layered semiconductors has relied on a back‐gated transistor architecture. This is useful for initial assessment but lacks ultimate compatibility with integrated circuit (IC) design since the threshold voltage of individual devices cannot be controlled independently in order to achieve specific ON‐state and OFF‐state performance. Note that threshold engineering via gate electrostatics is inevitable for 2D semiconductors owing to the absence of comprehensive, reliable, and universal doping schemes. In recent years, several strategies are adopted for the gating of individual 2D‐FETs such as atomic layer deposition (ALD) of high‐
k dielectrics, drop casting of ionic liquids, and deterministic transfer of insulating 2D hexagonal boron nitride. These techniques have their respective strengths and weaknesses. A facile, low‐temperature, scalable, and universally applicable fabrication scheme for dual‐gated monolayer 2D‐FETs is reported here, which is compatible with the back‐end‐of‐the‐line (BEOL) process flow of complementary metal oxide semiconductor (CMOS) technology, using hydrogen silsesquioxane (HSQ). HSQ is a negative tone resist that possesses dielectric properties similar to SiO2when exposed to high electron beam irradiation and thermal curing and can produce features as small as 10 nm.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/nano.202200091
