화학공학소재연구정보센터
Journal of the Electrochemical Society, Vol.146, No.10, 3716-3723, 1999
Low temperature metallorganic chemical vapor deposition routes to chromium metal thin films using bis(benzene)chromium
Different routes to control carbon incorporation into Cr-based coatings grown by metallorganic chemical vapor deposition (MOCVD) using Cr(C6H6)(2) as precursor have been explored. In agreement with partial equilibrium thermodynamic calculations, the reduction and even the suppression of carbon incorporation into the chromium layers from the decomposition of the input gas mixture Cr(C6H6)(2)/H-2 is possible only under or near atmospheric pressure. However. these deposition conditions do not allow for the development of a process for large scale applications since they lead to a poor uniformity and a low growth rate of the metal thin films. Hard chromium metal coatings are more conveniently deposited at low temperature (623-673 K) by addition of small amounts of C6Cl6 to the input gas phase. This MOCVD process operates at low pressure even with the use of inert carrier gas unlike the first route. Under these conditions, a good throwing power is obtained leading to a promising process for industrial applications. The influence of the growth conditions on the properties of the films is described, and some properties of the chromium coatings are presented. Interestingly, they exhibit a very high hardness (similar to 21 GPa) and good adhesion to steel substrates. A growth mechanism supported by on-line mass spectrometry analyses is discussed. The C6Cl6 molecules favor a reaction pathway which is not expected on the basis of predictions from thermodynamic calculation. The successful growth of vanadium metal thin films from bis(benzene)vanadium and C6Cl6 under related conditions suggests that the proposed mechanism may be extended to the deposition of other transition metals starling from their bis(arene)metal complexes as precursors.