Structure and bonding in amorphous iron carbide thin films

We investigate the amorphous structure, chemical bonding, and electrical properties of magnetron sputtered Fe(1-xCx) (0.21 ⩽ x ⩽ 0.72) thin films. X-ray, electron diffraction and transmission electron microscopy show that the Fe(1-xCx) films are amorphous nanocomposites, consisting of a two-phase domain structure with Fe-rich carbidic FeC(y), and a carbon-rich matrix. Pair distribution function analysis indicates a close-range order similar to those of crystalline Fe(3)C carbides in all films with additional graphene-like structures at high carbon content (71.8 at% C). From x-ray photoelectron spectroscopy measurements, we find that the amorphous carbidic phase has a composition of 15-25 at% carbon that slightly increases with total carbon content. X-ray absorption spectra exhibit an increasing number of unoccupied 3d states and a decreasing number of C 2p states as a function of carbon content. These changes signify a systematic redistribution in orbital occupation due to charge-transfer effects at the domain-size-dependent carbide/matrix interfaces. The four-point probe resistivity of the Fe(1-xCx) films increases exponentially with carbon content from ∼200 μΩ cm (x = 0.21) to ∼1200 μΩ cm (x = 0.72), and is found to depend on the total carbon content rather than the composition of the carbide. Our findings open new possibilities for modifying the resistivity of amorphous thin film coatings based on transition metal carbides through the control of amorphous domain structures.