Film formation using dimensional reduction

The process for film formation using a dimensional reduction approach requires three conceptually simple steps (Fig. 3.2). The first step involves... 

Figure 3.2. Film formation using a dimensional reduction approach involves three steps 1) breaking up the insoluble extended inorganic framework (a) into more soluble-isolated anionic species, which are separated by some small and volatile cationic species (b). 2) Solution-processing thin films of the precursor (b). 3) Heating the precursor films such that the cationic species and corresponding chalcogen anions are dissociated, leaving behind the targeted inorganic semiconductor (c).

In a similar way, electrochemistry may provide an atomic level control over the deposit, using electric potential (rather than temperature) to restrict deposition of elements. A surface electrochemical reaction limited in this manner is merely underpotential deposition (UPD see Sect. 4.3 for a detailed discussion). In ECALE, thin films of chemical compounds are formed, an atomic layer at a time, by using UPD, in a cycle thus, the formation of a binary compound involves the oxidative UPD of one element and the reductive UPD of another. The potential for the former should be negative of that used for the latter in order for the deposit to remain stable while the other component elements are being deposited. Practically, this sequential deposition is implemented by using a dual bath system or a flow cell, so as to alternately expose an electrode surface to different electrolytes. When conditions are well defined, the electrolytic layers are prone to grow two dimensionally rather than three dimensionally. ECALE requires the definition of precise experimental conditions, such as potentials, reactants, concentration, pH, charge-time, which are strictly dependent on the particular compound one wants to form, and the substrate as well. The problems with this technique are that the electrode is required to be rinsed after each UPD deposition, which may result in loss of potential control, deposit reproducibility problems, and waste of time and solution. Automated deposition systems have been developed as an attempt to overcome these problems. 

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