Hard X-ray photoelectron spectroscopy study of copper formation by metal salt inclusion in a polymer film

In this work we present the results of a Hard X-ray Photoelectron Spectroscopy (HAXPES) study on the creation of metallic copper layers via metal-salt infiltration into a poly-2-vinylpyridine (P2VP) film. Metal salt inclusion is a wet chemistry process which allows for the fabrication of both metal and metal oxide films by means of infiltrating a receptive polymer thin film with metal salt precursors. A copper infiltrated P2VP film was subject to UV/Ozone treatment to form copper oxide and annealed in-vacuo to reduce the film to metallic copper. HAXPES and transmission electron microscope (TEM) measurements were used to study the polymer film before and after metal salt infiltration, along with analysis of the copper oxide created after UV/Ozone treatment. The results show successful infiltration of the metal salt into the polymer film, as well as complete conversion to copper oxide following UV/Ozone treatment and reduction to metallic copper with a subsequent in-situ anneal, which demonstrates the ability of the technique for the creation of several key integrated circuit features

Growth chemistry and electrical performance of ultrathin alumina formed by area selective vapor phase infiltration

The growth chemistry and electrical performance of 5 nm alumina films, fabricated via the area-selective vapor phase infiltration (VPI) of trimethylaluminum into poly(2-vinylpyridine), are compared to a conventional plasma enhanced atomic layer deposition (PEALD) process. The chemical properties are assessed via energy dispersive X-ray spectroscopy and hard X-ray photoelectron spectroscopy measurements, while current – voltage dielectric breakdown and capacitance – voltage analysis is undertaken to provide electrical information of these films for the first time. The success and challenges in dielectric formation via polymer VPI, the compatibility of pyridine in such a role, and the ability of the unique and rapid grafting-to polymer brush method in forming coherent metal oxides is evaluated. It was found that VPI made alumina fabricated at temperatures between 200 and 250 °C had a consistent breakdown electrical field, with the best performing devices possessing a к value of 5.9. The results indicate that the VPI approach allows for the creation of alumina films that display dielectric properties of a comparable quality to conventional PEALD grown films

Aluminium oxide formation via atomic layer deposition using a polymer brush mediated selective infiltration approach

Area selective deposition (ASD) is an emerging method for the patterning of electronic devices as it can significantly reduce processing steps in the industry. A potential ASD methodology uses infiltration of metal precursors into patterned polymer materials. The work presented within demonstrates this potential by examining hydroxy terminated poly(2-vinylpyridine) (P2VP-OH) as the \u27receiving\u27 polymer and trimethylaluminium (TMA) and H2O as the material precursors in a conventional atomic layer deposition (ALD) process. Fundamental understanding of the surface process was achieved using X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) mapping via transmission electron microscopy (TEM). The resulting analysis confirms aluminium inclusion within the polymer film. Spectroscopic and microscopic characterisation show metal infiltration throughout the polymer to the underlying silicon dioxide interface. Exposing the infiltrated film to an oxygen plasma results in the removal of the organic component and resultant fabrication of a sub 5 nm aluminium oxide layer

Precise definition of a ‘monolayer point’ in polymer brush films for fabricating highly coherent TiO2 thin films by vapor phase Infiltration

In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2–4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings