Passive films electronic properties

The alloy composition (and microstructure) has strong effects on all the aspects of passivity that have been described above chemical composition and thickness of the passive film, electronic properties, structure, and kinetics of formation. The influence of alloyed elements on the electrochemical characteristics of passive systems can be seen in Fig. 3-16. This is the same current-potential curve as in Fig. 3-1, on which the two major effects of alloyed elements are indicated lowering of the dissolution current in the active region and at the active-passive transition, and broadening of the passive region. A third effect, not illustrated in Fig. 3-16 but which will be discussed later, is the improvement of the resistance of the alloy to passivity breakdown and localized corrosion. For iron-based alloys, these beneficial effects are obtained with chromium, molybdenum, nickel, and nitrogen. 

The anodic partial reaction also involves a charge transfer at the interface because a metal atom loses electrons. It then dissolves in the solution as a hydrated or complexed ion and diffuses towards the bulk. In the vicinity of the metal surface, the concentration generated by dissolution therefore often exceeds that of the bulk electrolyte. Once the solubility threshold is reached, solid reaction products begin to precipitate and form a porous film. Alternatively, under certain conditions, metal ions do not dissolve at all but form a thin compact oxide layer, called passive film. The properties of the passive film then determine the rate of corrosion of the underlying metal (Chapter 6). 

As outlined above, electron transfer through the passive film can also be cmcial for passivation and thus for the corrosion behaviour of a metal. Therefore, interest has grown in studies of the electronic properties of passive films. Many passive films are of a semiconductive nature [92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102 and 1031 and therefore can be investigated with teclmiques borrowed from semiconductor electrochemistry—most typically photoelectrochemistry and capacitance measurements of the Mott-Schottky type [104]. Generally it is found that many passive films cannot be described as ideal but rather as amorjDhous or highly defective semiconductors which often exlribit doping levels close to degeneracy [105]. 

The nature of the passive film has been the object of innumerable further studies with arguments over its thickness, composition, structure and electronic properties raging. What has become very clear is that that removal from solution and drying of the passivated electrode alters the film profoundly and any studies of the film ex situ must be treated with considerable caution. For that reason we will concentrate here primarily on in situ studies or at the least those studies carried out on passive films that retain their hydration. 

The electrochemical properties of passive layers lead to the question of their structure on a mesoscopic scale and at atomic resolution. Their barrier character with respect to metal corrosion postulates a dense, poreless film their electronic properties, in some cases, crystalline structures. The change of their properties with film aging, as in e.g. film-breakdown phenomena, support the existence of many defects that may heal with time. In many cases an amorphous structure is assumed. Some ex situ... 

A New Model. The results of the studies on anodic oxide films (see section 5.9 and chapter 3 on passive film and anodic oxides) show that anodic oxide properties (oxidation state, degree of hydration, 0/Si ratio, degree of crystallinity, electronic and ionic conductivities, and etch rate) are a function of the formation field (the applied potential). Also, they vary from the surface to the oxide/silicon interface, which means that they change with time as the layer of oxide near the oxide/silicon interface moves to the surface during the formation and dissolution process. The oxide near the silicon/oxide interface is more disordered in composition and structure than that in the bulk of the oxide film. Also, the degree of disorder depends on the formation field which is a function of thickness and potential. The range of disorder in the oxide stmcture is thus responsible for the variation in the etch rate of the oxide formed at different times during a period of the oscillation. The etch rate of silicon oxides is very sensitive to the stmcture and composition (see Chapter 4). 

STM offers the possibility of performing local spectroscopic measurements (/ vs. V curves). These measurements can be performed in-situ and ex-situ. Ex-situ UHV conditions are however more appropriate to ensure the nonconductivity of the turmeling barrier between surface and tip. Such measurements on passive films formed on Ni and Cr should provide valuable information on the conductivity of the films. This is a promising perspective for the local characterization with high resolution of the electronic properties of passive films. On the subject of the relation between chemistry at the atomic scale and atomic structure, the STM results on the passive film formed on Ni also show promising perspectives for further characterization accurate bias-dependent measurements of the terraces of the NiO oxide should provide... 

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