Passivity thin film

T. J. Courts, Ed., Active and Passive Thin Film Devices. Academic Press, London, 1978. 

Klein R. M., Chalcogenide glasses as passive thin-film structures for integrated optics,/. Electron. Mater., 3, 79-99 (1974). 

In most cases, CVD reactions are activated thermally, but in some cases, notably in exothermic chemical transport reactions, the substrate temperature is held below that of the feed material to obtain deposition. Other means of activation are available (7), eg, deposition at lower substrate temperatures is obtained by electric-discharge plasma activation. In some cases, unique materials are produced by plasma-assisted CVD (PACVD), such as amorphous siHcon from silane where 10—35 mol % hydrogen remains bonded in the soHd deposit. Except for the problem of large amounts of energy consumption in its formation, this material is of interest for thin-film solar cells. Passivating films of Si02 or Si02 Si N deposited by PACVD are of interest in the semiconductor industry (see Semiconductors). 

Use and Uimitations of Electrochemical Techniques A major caution must be noted as to the general, indiscriminate use of all electrochemical tests, especially the use of AC and EIS test techniques, for the study of corrosion systems. AC and EIS techniques are apphcable for the evaluation of very thin films or deposits that are uniform, constant, and stable—for example, thin-film protective coatings. Sometimes, researchers do not recognize the dynamic nature of some passive films, corrosion produc ts, or deposits from other sources nor do they even consider the possibility of a change in the surface conditions during the course of their experiment. As an example, it is note-... 

Metals that depend on a relatively thick protective coating of corrosion product for corrosion resistance are frequently subject to erosion-corrosion. This is due to the poor adherence of these coatings relative to the thin films formed by the classical passive metals, such as stainless steel and titanium. Both stainless steel and titanium are relatively immune to erosion-corrosion in most cooling water environments. 

This work has been carried out by Marcus and his co-workersand deals with the influence of sulphur on the passivation of Ni-Fe alloys. For sulphur-containing Ni-Fe alloys, sulphur segregates on the surface during anodic dissolution. Above a critical sulphur content a non-protective thin sulphide film is formed on the surface instead of the passive oxide film. 

The outstanding characteristics of the noble metals are their exceptional resistance to corrosive attack by a wide range of liquid and gaseous substances, and their stability at high temperatures under conditions where base metals would be rapidly oxidised. This resistance to chemical and oxidative attack arises principally from the Inherently high thermodynamic stability of the noble metals, but in aqueous media under oxidising or anodic conditions a very thin film of adsorbed oxygen or oxide may be formed which can contribute to their corrosion resistance. An exception to this rule, however, is the passivation of silver and silver alloys in hydrochloric or hydrobromic acids by the formation of relatively thick halide films. 

Since the natural passivity of aluminium is due to the thin film of oxide formed by the action of the atmosphere, it is not unexpected that the thicker films formed by anodic oxidation afford considerable protection against corrosive influences, provided the oxide layer is continuous, and free from macropores. The protective action of the film is considerably enhanced by effective sealing, which plugs the mouths of the micropores formed in the normal course of anodising with hydrated oxide, and still further improvement may be afforded by the incorporation of corrosion inhibitors, such as dichromates, in the sealing solution. Chromic acid films, in spite of their thinness, show good corrosion resistance. 

The current-potential relationship ABCDE, as obtained potentiosta-tically, has allowed a study of the passive phenomena in greater detail and the operational definition of the passive state with greater preciseness. Bonhoeffer, Vetter and many others have made extensive potentiostatic studies of iron which indicate that the metal has a thin film, composed of one or more oxides of iron, on its surface when in the passive state . Similar studies have been made with stainless steel, nickel, chromium and other metals... 

The reason a passive film is so thin is that the film is formed at a potential that is not far from the range where water molecules are stable. This is also the reason the same thin film is immediately repaired after... 

A thick is deposited on top. This is then covered with a molecularly thin film of lubricant to minimize wear during start-stop contacts and to passivate the disc surface against contamination and corrosion. High-molecular-weight perfluoropolyalkylether (PFPE) polymers are widely used for this purpose. In order to improve surface bonding, the PFPEs are modified with specific functional end groups. All these molecules have similar backbone structures, namely ... 

The optical properties of electrodeposited, polycrystalline CdTe have been found to be similar to those of single-crystal CdTe [257]. In 1982, Fulop et al. [258] reported the development of metal junction solar cells of high efficiency using thin film (4 p,m) n-type CdTe as absorber, electrodeposited from a typical acidic aqueous solution on metallic substrate (Cu, steel, Ni) and annealed in air at 300 °C. The cells were constructed using a Schottky barrier rectifying junction at the front surface (vacuum-deposited Au, Ni) and a (electrodeposited) Cd ohmic contact at the back. Passivation of the top surface (treatment with KOH and hydrazine) was seen to improve the photovoltaic properties of the rectifying junction. The best fabricated cell comprised an efficiency of 8.6% (AMI), open-circuit voltage of 0.723 V, short-circuit current of 18.7 mA cm, and a fill factor of 0.64. 

Ham D, Mishra KK, Rajeshwar K (1991) Anodic electrosynthesis of cadmium selenide thin films. Characterization and comparison with the passive/transpassive behavior of the CdX (X = S, Te) counterparts. J Electrochem Soc 138 100-108 Stimming U (1985) Photoelectrochemical studies of passive films (Review Article). Electrochim Acta 31 ... 

Environmental tests have been combined with conventional electrochemical measurements by Smallen et al. [131] and by Novotny and Staud [132], The first electrochemical tests on CoCr thin-film alloys were published by Wang et al. [133]. Kobayashi et al. [134] reported electrochemical data coupled with surface analysis of anodically oxidized amorphous CoX alloys, with X = Ta, Nb, Ti or Zr. Brusic et al. [125] presented potentiodynamic polarization curves obtained on electroless CoP and sputtered Co, CoNi, CoTi, and CoCr in distilled water. The results indicate that the thin-film alloys behave similarly to the bulk materials [133], The protective film is less than 5 nm thick [127] and rich in a passivating metal oxide, such as chromium oxide [133, 134], Such an oxide forms preferentially if the Cr content in the alloy is, depending on the author, above 10% [130], 14% [131], 16% [127], or 17% [133], It is thought to stabilize the non-passivating cobalt oxides [123], Once covered by stable oxide, the alloy surface shows much higher corrosion potential and lower corrosion rate than Co, i.e. it shows more noble behavior [125]. 

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