Atomic layer deposition (ALD) technique is used in the preparation of organic/inorganic layers, which requires uniform surfaces with their thickness down to several nanometers. For film with such thickness, the growth mode defined as the arrangement of clusters on the surface during the growth is of significance. In this work, Al2O3 thin film was deposited on various interfacial species of pre-treated polyethylene terephthalate (PET, 12 µm) by plasma assisted atomic layer deposition (PA-ALD), where trimethyl aluminium was used as the Al precursor and O2 as the oxygen source. The interfacial species, -NH3, -OH, and -COOH as well as SiCHO (derived from monomer of HMDSO plasma), were grafted previously by plasma and chemical treatments. The growth mode of PA-ALD Al2O3 was then investigated in detail by combining results from in-situ diagnosis of spectroscopic ellipsometry (SE) and ex-situ characterization of as-deposited layers from the morphologies scanned by atomic force microscopy (AFM). In addition, the oxygen transmission rates (OTR) of the original and treated plastic films were measured. The possible reasons for the dependence of the OTR values on the surface species were explored.
In this paper, Al 2 O 3 thin films are deposited on a hydrogen-terminated Si substrate by using two home-built electron cyclotron resonance (ECR) and magnetic field enhanced radio frequency plasma-assisted atomic layer deposition (PA-ALD) devices with Al(CH 3) 3 (trimethylaluminum, TMA) and oxygen plasma used as precursor and oxidant, respectively. The thickness, chemical composition, surface morphology and group reactions are characterized by in situ spectroscopic ellipsometer, x-ray photoelectric spectroscopy, atomic force microscopy, scanning electron microscopy, a high-resolution transmission electron microscope and in situ mass spectrometry (MS), respectively. We obtain that both ECR PA-ALD and the magnetic field enhanced PA-ALD can deposit thin films with high density, high purity, and uniformity at a high deposition rate. MS analysis reveals that the Al 2 O 3 deposition reactions are not simple reactions between TMA and oxygen plasma to produce alumina, water and carbon dioxide. In fact, acetylene, carbon monoxide and some other by-products also appear in the exhaustion gas. In addition, the presence of bias voltage has a certain effect on the deposition rate and surface morphology of films, which may be attributed to the presence of bias voltage controlling the plasma energy and density. We conclude that both plasma sources have a different deposition mechanism, which is much more complicated than expected.
Metal aluminum (Al) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited Al films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.
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