Role of a cyclopentadienyl ligand in a heteroleptic alkoxide precursor in atomic layer deposition.
The Journal of chemical physics
2024; 160 (2)
Alkoxide precursors have been highlighted for depositing carbon-free films, but their use in Atomic Layer Deposition (ALD) often exhibits a non-saturated growth. This indicates no self-limiting growth due to the chain reaction of hydrolysis or ligand decomposition caused by β-hydride elimination. In the previous study, we demonstrated that self-limiting growth of ALD can be achieved using our newly developed precursor, hafnium cyclopentadienyl tris(N-ethoxy-2,2-dimethyl propanamido) [HfCp(edpa)3]. To elucidate the growth mechanism and the role of cyclopentadienyl (Cp) ligand in a heteroleptic alkoxide precursor, herein, we compare homoleptic and heteroleptic Hf precursors consisting of N-ethoxy-2,2-dimethyl propanamido (edpa) ligands with and without cyclopentadienyl ligand-hafnium tetrakis(N-ethoxy-2,2-dimethyl propanamido) [Hf(edpa)4] and HfCp(edpa)3. We also investigate the role of a Cp ligand in growth characteristics. By substituting an alkoxide ligand with a Cp ligand, we could modify the surface reaction during ALD, preventing undesired reactions. The last remaining edpa after Hf(edpa)4 adsorption can undergo a hydride elimination reaction, resulting in surface O-H generation. In contrast, Cp remains after the HfCp(edpa)3 adsorption. Accordingly, we observe proper ALD growth with self-limiting properties. Thus, a comparative study of different ligands of the precursors can provide critical clues to the design of alkoxide precursors for obtaining typical ALD growth with a saturation behavior.
View details for DOI 10.1063/5.0182690
View details for PubMedID 38189606
Area-Selective Atomic Layer Deposition for Resistive Random-Access Memory Devices.
ACS applied materials & interfaces
Resistive random-access memory (RRAM) is a promising technology for data storage and neuromorphic computing; however, cycle-to-cycle and device-to-device variability limits its widespread adoption and high-volume manufacturability. Improving the structural accuracy of RRAM devices during fabrication can reduce these variabilities by minimizing the filamentary randomness within a device. Here, we studied area-selective atomic layer deposition (AS-ALD) of the HfO2 dielectric for the fabrication of RRAM devices with higher reliability and accuracy. Without requiring photolithography, first we demonstrated ALD of HfO2 patterns uniformly and selectively on Pt bottom electrodes for RRAM but not on the underlying SiO2/Si substrate. RRAM devices fabricated using AS-ALD showed significantly narrower operating voltage range (2.6 × improvement) and resistance states than control devices without AS-ALD, improving the overall reliability of RRAM. Irrespective of device size (1 × 1, 2 × 2, and 5 × 5 μm2), we observed similar improvement, which is an inherent outcome of the AS-ALD technique. Our demonstration of AS-ALD for improved RRAM devices could further encourage the adoption of such techniques for other data storage technologies, including phase-change, magnetic, and ferroelectric RAM.
View details for DOI 10.1021/acsami.3c05822
View details for PubMedID 37656599
- Dysprosium Incorporation for Phase Stabilization of Atomic-Layer- Deposited HfO2 Thin Films CHEMISTRY OF MATERIALS 2023