Oxides chemical dissolution

The mechanisms of oxide dissolution and scale removal have been widely studied in recent years. This work has been thoroughly reviewed by Frenier and Growcock who concluded, in agreement with others", that oxide removal from the surface of steel occurs predominantly by a process of reductive dissolution, rather than by chemical dissolution, which is slow in mineral acids. 

In general there does not appear to be any direct correlation between the rate of the chemical dissolution of oxides and the rate of scale removal, although most work on oxide dissolution has concentrated on magnetite. For example, Gorichev and co-workers have studied the kinetics and mechanisms of dissolution of magnetite in acids and found that it is faster in phosphoric acid than in hydrochloric, whereas scale removal is slower. Also, ferrous ions accelerate the dissolution of magnetite in sulphuric, phosphoric and hydrochloric acid , whereas the scale removal rate is reduced by the addition of ferrous ions. These observations appear to emphasise the importance of reductive dissolution and undermining in scale removal, as opposed to direct chemical dissolution. 

An answer to the first question may be found in noting that the electric field in a thin oxide film is different from that in a thick one and that weakening of electrostatic repulsion which prevents hydration and withdrawal of the O/S interface from the surface is a prerequisite for chemical dissolution. 

However, this does not preclude the possibility that in a portion of the oxide at least (the outer layer), the OH transport mechanism is operative, with the release of protons at the interface between the two oxide layers. Hence, in such a case, some field-assisted proton transfer is likely to take place through the outer layer while chemical dissolution should be operative at the outer O/S interface. 

When the surface is completely covered by an oxide film, dissolution becomes independent of the geometric factors such as surface curvature and orientation, which are responsible for the formation and directional growth of pores. Fundamentally, unlike silicon, which does not have an atomic structure identical in different directions, anodic silicon oxides are amorphous in nature and thus have intrinsically identical structure in all orientations. Also, on the oxide covered surface the rate determining step is no longer electrochemical but the chemical dissolution of the oxide.1... 

When the pore bottom is covered by an oxide, the change of applied potential occurs almost completely in the oxide due to the very high resistance of the oxide. The rate of reactions is now limited by the chemical dissolution of the oxide on the oxide covered area. When the entire pore bottom is covered with an oxide the rate of reaction is the same on the entire surface of the pore bottom. As a result, the bottom flattens and the condition for PS formation disappears. The change of oxide coverage on the pore bottom can also occur when diffusion of the electrolyte inside deep pores becomes the rate limiting process. Since the current at which formation of an oxide occurs increases with HF concentration, a decreased HF concentration at pore bottom due to the diffusion effect can result in the formation of an oxide on the pore bottom of a deep pore at a condition that does not occur in shallow pores. 

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. 

If the anodic potential is increased, the current density becomes larger than JPS and dissolution occurs via an intermediate anodic oxide film. Hence the reaction can be separated into electrochemical oxide formation according to reaction (4.2) and chemical dissolution of the oxide due to HF, (HF)2 or HF2 [So2] ... 

The first of the four characteristic currents to J4 has a prominent position. It indicates the crossover from a charge supply limited reaction to a kmetically and mass transfer limited reaction. This crossover is accompanied by pronounced changes in charge state, chemical dissolution reaction, dissolution valence, pore formation and anodic oxide formation. Therefore its dependence on other parameters, such as crystal orientation, temperature or H F concentration deserves further investigation. In the literature Jt is usually termed /crl JPS or JPSL. In the following the symbol JPS will be used. 

Electron injection has been observed during the chemical dissolution of an oxide film in HF [Mai, Ozl, Bi5]. The injected electrons are easily detected if the anodized electrode is n-type and kept in the dark. Independently of oxide thickness and whether the oxide is thermally grown or formed by anodization, injected electrons are only observed during the dissolution of the last few monolayers adjacent to the silicon interface. The electron injection current transient depends on dissolution rate respectively HF concentration, however, the exchanged charge per area is always in the order of 0.6 mC cm-2. This is shown in Fig. 4.14 for an n-type silicon electrode illuminated with chopped light. The transient injection current is clearly visible in the dark phases. 

If a silicon electrode is anodically oxidized in an acidic electrolyte free of HF, the oxide thickness increases monotonically with anodization time. This is also true for alkaline electrolytes if the oxide formation rate exceeds the slow chemical dissolution of the anodic Si02. This monotonic behavior, however, is not necessarily associated with monotonic current-time or potential-time curves. 

CMP processes for oxide planarization (ILD and STI) rely on slurry chemistry to hydrolyze and soften the Si02 surface. Mechanical abrasion then controls the actual material removal. Thus, the key process output control variables (i.e., removal rate and nonuniformity) are strong functions of the mechanical properties of the system, namely, the down force and the relative velocity between the pad and the wafer. Metal CMP processes such as copper CMP rely more on chemical oxidation and dissolution of the metal than mechanical abrasion to remove the metal overburden. Consequently, careful control of the chemistry of the CMP process is more important for these CMP processes than it is for oxide CMP. Thus, CMP tools and processes optimized for ILD may not be optimal for metal CMP and vice versa. 

The surface films react chemically with solution species, thus leading to their dissolution as reaction products [17]. Surface species such as oxides, hydroxides, and nitrides may be highly nucleophilic, while many polar aprotic solvents are highly electrophilic. Hence, chemical dissolution of pristine surface films on active metals in solutions is a very probable route [18]. 

In addition, there are several important chemical processes in electrochemically assisted coagulation. The more important is the chemical dissolution which consists of the oxidation of the metal sheets with the simultaneous reduction of water to form hydrogen. This process is represented by (4.52). 

Alloy dissolution — The process of anodic oxidation of an alloy electrode by application of a suitable - electrode potential. It leads to dissolved products. Under non-electrochemical conditions the dissolution of an alloy can be performed with a chemical oxidant The rate of dissolution depends on the structure and homogeneity of the processed material. When the applied potential or, in the case of chemical dissolution, the oxidation potential of the chemical oxidant lays between the formal potentials of the dissolved components, a selective... 

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