Search

We demonstrate a polymer brush assisted approach for the fabrication of continuous zirconium oxide (ZrO2) films over large areas with high uniformity (pin-hole free) on copper (Cu) substrates. This approach involves the use of a thiol-terminated polymethyl methacrylate brush (PMMA-SH) as the template layer for the selective infiltration of zirconium oxynitrate (ZrN2O7). The preparation of a highly uniform covalently grafted polymer monolayer on the Cu substrate is the critical factor in fabricating a metal oxide film of uniform thickness across the surface. Infiltration is reliant on the chemical interactions between the polymer functional group and the metal precursor. A following reductive H2 plasma treatment process results in ZrO2 film formation whilst the surface Cu2O passive oxide layer was reduced to a Cu/Cu2O interface. Fundamental analysis of the infiltration process and the resulting ZrO2 film was determined by XPS, and GA-FTIR. Results derived from these techniques confirm the inclusion of the ZrN2O7 into the polymer films. Cross-sectional transmission electron microscopy and energy dispersive X-ray mapping analysis corroborate the formation of ZrO2 layer at Cu substrate. We believe that this quick and facile methodology to prepare ZrO2 films is potentially scalable to other high-κ dielectric materials of high interest in microelectronic applications.

Fabrication of ultrathin films of dielectric (with particular reference to materials with high dielectric constants) materials has significance in many advanced technological applications including hard protective coatings, sensors, and next-generation logic devices. Current state-of-the-art in microelectronics for fabricating these thin films is a combination of atomic layer deposition and photolithography. As feature size decreases and aspect ratios increase, conformality of the films becomes paramount. Here, we show a polymer brush template-assisted deposition of highly conformal, ultrathin (sub 5 nm) high-κ dielectric metal oxide films (hafnium oxide and zirconium oxide) on topographically patterned silicon nitride substrates. This technique, using hydroxyl terminated poly-4-vinyl pyridine (P4VP-OH) as the polymer brush, allows for conformal deposition with uniform thickness along the trenches and sidewalls of the substrate. Metal salts are infiltrated into the grafted monolayer polymer brush films via solution deposition. Tailoring specific polymer interfacial chemistries for ion infiltration combined with subsequent oxygen plasma treatment enabled the fabrication of high-quality sub 5 nm metal oxide films.