Passivation in Alkaline Solutions

The form of Figure 1.43 is common among many metals in solutions of acidic to neutral pH of non-complexing anions. Some metals such as aluminium and zinc, whose oxides are amphoteric, lose their passivity in alkaline solutions, a feature reflected in the potential/pH diagram. This is likely to arise from the rapid rate at which the oxide is attacked by the solution, rather than from direct attack on the metal, although at low potential, active dissolution is predicted thermodynamically The reader is referred to the classical work of Pourbaix for a full treatment of potential/pH diagrams of pure metals in equilibrium with water. 

If the applied current density is reduced when a tin anode has been made passive in alkaline solution with the formation of a brown him and evolution of oxygen, the surface him changes to one of yellow colour and dissolution of tin as stannite ions proceeds freely . This effect is exploited in the electrodeposition of tin from sodium or potassium stannate solutions. 

But even in a homogeneously doped material an etch stop layer can be generated by an inhomogeneous charge carrier distribution. If a positive bias is applied to the metal electrode of an MOS structure, an inversion layer is formed in the p-type semiconductor. The inversion layer passivates in alkaline solutions if it is kept at the PP using a second bias [Sm5], as shown in Fig. 4.16b. This method is used to reduce the thickness variations of SOI wafers [Og2]. Illuminated regions... 

A prerequisite for all etch-stop techniques discussed so far is an electrical connection to an external power supply. However, if the potential required for passivation in alkaline solutions is below 1 V, it can be generated by an internal galvanic cell, for example by a gold-silicon element [As4, Xil]. An internal galvanic cell can also be realized by a p-n junction illuminated in the etchant, as discussed in the next section. Internal cells eliminate the need for external contacts and make this technique suitable for simple batch fabrication. 

An illuminated area on n-type Si is anodically passivated in alkaline solutions for potentials in excess of PP, whereas an area kept in the dark is not passivated and is therefore etched with the OCP etch rate. 

Shortly after initiation of charge, hydrogen evolution begins on the iron electrode. The considerable hydrogen evolution on charge presumably helps counteract iron passivation in alkaline solution. Mercury additions also have a similar effect, but only in the early formation cycles. 

In alkaline solutions of pH >10.45, Mg tends to passivate in alkaline solutions at pH> 10.45, and at more alkaline pH sueh as 13 (O.IM NaOH) a truly passive behaviour is expected (Fig. 2.5). An average eurrent density of a few p,A/cm is observed in the passive region at a relatively high sean rate 1 mV/s. 

In alkaline solutions, corrosion of steel is controlled by the rate of oxygen diffusion through the precipitated corrosion product (usually ferrous hydroxide, Fe(OH)2), so corrosion rates are low. Steel is easily passivated in alkaline solutions. Amphoteric metals such as aluminum, zinc, and lead corrode slowly at low alkali concentrations, but above pH 9.0 their rates are very high and inhibitors are required. 

Variations in pH promoted increases in corrosion potentials from acid pH levels to neutral pH thereafter, however, corrosion potentials were lowered in alkaline solutions to more active values. Decreasing pH caused a lowering of breakdown potentials in the presence of Cl and an increase in the current densities for passivation. 

In alkaline solutions, except possibly in high concentrations at elevated temperatures, nickel is normally passive. 

In acidic solutions the film has been reported to be hydrated nickel oxyhydroxide, NiOy(OH)2 2y. MH2O in which y is greater in the passive film than in the pre-passive film formed in the active region . In neutral solutions films consisting of NiO and Ni(OH)2 possibly with some NiO have been described. In alkaline solutions NifOHlj has been reported . 

Tin when made anodic shows passive behaviour as surface films are built up but slow dissolution of tin may persist in some solutions and transpassive dissolution may occur in strongly alkaline solutions. Some details have been published for phosphoric acid with readily obtained passivity, and sulphuric acid " for which activity is more persistent, but most interest has been shown in the effects in alkaline solutions. For galvanostatic polarisation in sodium borate and in sodium carbonate solutions at 1 x 10" -50 X 10" A/cm, simultaneous dissolution of tin as stannite ions and formation of a layer of SnO occurs until a critical potential is reached, at which a different oxide or hydroxide (possibly SnOj) is formed and dissolution ceases. Finally oxygen is evolved from the passive metal. The nature of the surface films formed in KOH solutions up to 7 m and other alkaline solutions has also been examined. 

Unlike the cathodic reaction, anodic oxidation (ionization) of molecular hydrogen can be studied for only a few electrode materials, which include the platinum group metals, tungsten carbide, and in alkaline solutions nickel. Other metals either are not sufficiently stable in the appropriate range of potentials or prove to be inactive toward this reaction. For the materials mentioned, it can be realized only over a relatively narrow range of potentials. Adsorbed or phase oxide layers interfering with the reaction form on the surface at positive potentials. Hence, as the polarization is raised, the anodic current will first increase, then decrease (i.e., the electrode becomes passive see Fig. 16.3 in Chapter 16). In the case of nickel and tungsten... 

A passive film is formed on the Mg electrode surface in alkaline solutions, which creates problems when the Mg-air cell is to be discharged. However Mg and especially some Mg alloys are suitable to be used in magnesium-air cells with NaCl-electrolyte [4], where the formation of the passive film on the magnesium surface is not observed. 

Etching of silicon in alkaline solutions occurs under evolution of hydrogen with a ratio of two molecules H2 per dissolved Si atom. This ratio is found to be reduced under positive bias [Pa6] or by addition of oxidizing agents like H202 [Sc6], If the anodic bias is increased beyond the passivation potential (PP), the dissolution rate is reduced by orders of magnitude. 

In contrast to acidic electrolytes, chemical dissolution of a silicon electrode proceeds already at OCP in alkaline electrolytes. For cathodic potentials chemical dissolution competes with cathodic reactions, this commonly leads to a reduced dissolution rate and the formation of a slush layer under certain conditions [Pa2]. For potentials slightly anodic of OCP, electrochemical dissolution accompanies the chemical one and the dissolution rate is thereby enhanced [Pa6]. For anodic potentials above the passivation potential (PP), the formation of an anodic oxide, as in the case of acidic electrolytes, is observed. Such oxides show a much lower dissolution rate in alkaline solutions than the silicon substrate. As a result the electrode surface becomes passivated and the current density decreases to small values that correspond to the oxide etch rate. That the current density peaks at PP in Fig. 3.4 are in fact connected with the growth of a passivating oxide is proved using in situ ellipsometry [Pa2]. Passivation is independent of the type of cation. Organic compounds like hydrazin [Sul], for example, show a behavior similar to inorganic ones, like KOH [Pa8]. Because of the presence of a passivating oxide the current peak at PP is not observed for a reverse potential scan. 

As expected from the anisotropy of chemical etching of Si in alkaline solutions, the electrochemical dissolution reaction shows a strong dependence on crystal orientation. For all crystal orientations except (111) a sweep rate independent anodic steady-state current density is observed for potentials below PP. For (111) silicon electrodes the passivation peak becomes sweep rate dependent and corresponds to a constant charge of 2.4 0.5 mCcm-2 [Sm6]. OCP and PP show a slight shift to more anodic potentials for (111) silicon if compared to (100) substrates, as shown in Fig. 3.4. 

At higher anodic potentials an anodic oxide is formed on silicon electrode surfaces. This leads to a tetravalent electrochemical dissolution scheme in HF and to passivation in alkaline electrolytes. The hydroxyl ion is assumed to be the active species in the oxidation reaction [Drl]. The applied potential enables OH to diffuse through the oxide film to the interface and to establish an Si-O-Si bridge under consumption of two holes, according to Fig. 4.4, steps 1 and 2. Details of anodic oxide formation processes are discussed in Chapter 5. This oxide film passivates the Si electrode in aqueous solutions that are free of HF. 

More sophisticated than the use of an insulator to disconnect a part of the sample is the use of an electronic insulation realized by a p-n junction. Because the potential required to passivate a silicon electrode in alkaline solutions [Pa8] is smaller than the bias required to forward a junction, only the side of the junction that is connected will be passivated [Jal, Ge5], as shown in Fig. 4.16a. Note that a temporary... 

Small leakage currents or a transistor-like action of the junction are sufficient to generate a small current that may cause undesired passivation. This can be circumvented by application of an additional potential to the etching layer, shown by the broken line in Fig. 4.16 a. This electrochemical etch-stop technique is favorable compared to the conventional chemical p+ etch stop in alkaline solutions, because it does not require high doping densities. This etch stop has mainly been apphed for manufacturing thin silicon membranes [Ge5, Pa7, Kll] used for example in pressure sensors [Hil]. 

The third aspect to consider is the electrochemical stability of the material used. For the oxygen reduction reaction, the electrode potential is highly anodic and at this potential, most metals dissolve actively in acid media or form passive oxide films that will Inhibit this reaction. The oxide forming metals can form non-conducting or semi-conducting oxide films of variable thickness. In alkaline solutions, the range of metals that can be used is broader and can include non-precious or semi-precious metals (Ni, Ag). 

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