Inherently Area-Selective Atomic Layer Deposition of Manganese Oxide through Electronegativity-Induced Adsorption

Abstract

Manganese oxide (MnOx) shows great potential in the areas of nano-electronics, magnetic devices and so on. Since the characteristics of precise thickness control at the atomic level and self-align lateral patterning, area-selective deposition (ASD) of the MnOx films can be used in some key steps of nanomanufacturing. In this work, MnOx films are deposited on Pt, Cu and SiO2 substrates using Mn(EtCp)2 and H2O over a temperature range of 80–215 °C. Inherently area-selective atomic layer deposition (ALD) of MnOx is successfully achieved on metal/SiO2 patterns. The selectivity improves with increasing deposition temperature within the ALD window. Moreover, it is demonstrated that with the decrease of electronegativity differences between M (M = Si, Cu and Pt) and O, the chemisorption energy barrier decreases, which affects the initial nucleation rate. The inherent ASD aroused by the electronegativity differences shows a possible method for further development and prediction of ASD processes.

Surface Acidity-Induced Inherently Selective Atomic Layer Deposition of Tantalum Oxide on Dielectrics

“…For example, noble metals can dissociate oxygen into active species to promote ALD nucleation at low temperature, while inactive oxide surface has a long nucleation delay . The differences in surface electronegativity are also revealed to be a supplemental explanation for selective growth of MnO x between Pt and SiO 2 . It is discovered that the selective deposition of ZnO on Si/SiO 2 originates from a kinetically hindered surface reaction on H-terminated Si prior to OH-terminated SiO 2 .…”

“…It is necessary to explore inherently selective ALD as an important supplementary method, which relaxes process complexity. , Inherently selective ALD, which is free of inhibitors and removing steps, strongly relies on surface chemistry. , We have reported the inherently selective ALD of oxides on terrace and edge sites of metallic nanoparticles. The selectivity originates from intrinsic differences in binding energies of precursors on facets and low coordinated sites. − Adjusting the kinetic parameters, including temperature, precursor partial pressure, and selecting proper precursors, can extend the selective deposition window. − As for the selective ALD on different materials, various material combinations between metal, semiconductor or dielectrics are achieved, such as Ag and SiO 2 , Pt and SiO 2 , , α-Si:H and SiO 2 , − SiO 2 and SiN, , TiN and SiO 2 , , and so forth. These methods primarily rely on different surface functional groups, such as hydride versus hydroxyl and amino versus hydroxyl, and adjusting deposition temperature could also enlarge the differences of growth rate on these surfaces.…”

“…26−28 Adjusting the kinetic parameters, including temperature, precursor partial pressure, and selecting proper precursors, can extend the selective deposition window. 29−31 As for the selective ALD on different materials, various material combinations between metal, semiconductor or dielectrics are achieved, such as Ag and SiO 2 , 32 Pt and SiO 2 , 33,34 α-Si:H and SiO 2 , 35−38 SiO 2 and SiN, 39,40 TiN and SiO 2 , 41,42 and so forth. These methods primarily rely on different surface functional groups, such as hydride versus hydroxyl and amino versus hydroxyl, and adjusting deposition temperature could also enlarge the differences of growth rate on these surfaces.…”

“…33 The differences in surface electronegativity are also revealed to be a supplemental explanation for selective growth of MnO x between Pt and SiO 2 . 34 It is discovered that the selective deposition of ZnO on Si/SiO 2 originates from a kinetically hindered surface reaction on H-terminated Si prior to OHterminated SiO 2 . 36 The oxide versus nitride selectivity comes from the differences in activation energy of the precursor adsorbed on −OH versus −NH 2 surface groups.…”

Vapor-Phase Halogenation of Hydrogen-Terminated Silicon(100) Using N-Halogen-succinimides

“…Typical AS-ALD resists include polymeric − and inorganic − thin films. They are often deposited via traditional stencil lithography or photolithography, negating the potential high-resolution advantages of AS-ALD.…”