Guidance of growth mode and structural character in organic–inorganic hybrid materials – a comparative study

Abstract

A main goal in the construction of thin films is to control film growth in all aspects. Accurate control of the building blocks and their reaction sites is one way to achieve that. This is a key feature of the atomic layer deposition (ALD) technique. The aim of this study is to achieve such growth control of organic–inorganic thin films. The organic building blocks consist of the linear carboxylic acids: glutaric, tricarballylic, and trans-aconitic acid and the amino acid L-glutamic acid. All of these are based on five carbon long backbones. The acids were linked by aluminium using trimethylaluminum (TMA). These precursors made it possible to study the effect of the functionality of the organic acid backbone on growth rate, reaction modes, and the material properties of the deposited materials. The growth dynamics were investigated by in situ characterization using a quartz crystal microbalance (QCM). QCM revealed that all systems are of a self-limiting ALD-type. Ideal ALD growth was found for the tricarballylic acid–TMA system. For the other systems, the growth rate decreased with increasing temperature. The growth rates ranged from 0.05 to 2 nm per cycle. Analysis by Fourier transform infrared spectroscopy (FTIR) verified the hybrid character of the films and the presence of two different growth modes. The films were X-ray amorphous as deposited, with the exception of the L-glutamic–TMA system. Surface roughness and topography of the films was investigated by atomic force microscopy (AFM). Optical and surface wetting properties of the films were investigated by UV-Vis spectroscopy and the goniometer method for sessile drops, respectively. All films were stable in contact with water and generally had very low surface roughness. The present work has shown that the ALD technique can offer controlled growth of functionalized hybrid materials. It is likely that specifically chosen functionalized precursors can be employed to obtain specific structural designs and properties. The first sign of this was found for the L-glutamic–TMA system. The diffraction features of the as-deposited films of this system indicate the presence of sheet-like ordering within the material. This is one of the first observations of this kind by ALD.