Double -layer

The negative and positive charge densities at a metal surface. Because the valence electrons are relatively free, they extend farther from the surface than the ion core and therefore the surface shows a negative charge. (From Ref. (9)). 

For insulators and metals, charges accumulate at the surface as a result of adsorbed charge species. For instance, at the SiOj surface, dangling Si-0- bonds are passivated forming either the charged species Si-OHj or Si-0 or the neutral species Si-OH. Equilibrium between these species is given by  

The final type of boundary layer results from chemical reactions of metal surfaces with the slurry chemicals. During metal CMP, the slurry chemicals react with the metal surface and form either solid or ionic products or both. Such reactions are considered corrosion reactions. Formation of solid species occurs on the metal surface, forming a surface layer which, to varying de- 

Different surface films affect the diffusion of reactants and products differently however. As shall be discussed in Giapter 6, tungsten slurries are tailored to form WO3 on the tungsten surface during WO3 is a dense, nonporous film and therefore a 

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This produces a double layer of charge, one localized on the surface of the plane and the other developed in a diffuse region extending into solution. 

The treatment in the case of a plane charged surface and the resulting diffuse double layer is due mainly to Gouy and Qiapman. Here may be replaced by d /dx since is now only a function of distance normal to the surface. It is convenient to define the quantities y and yo as... 

The quantity 1 /k is thus the distance at which the potential has reached the 1 je fraction of its value at the surface and coincides with the center of action of the space charge. The plane at a = l//c is therefore taken as the effective thickness of the diffuse double layer. As an example, 1/x = 30 A in the case of 0.01 M uni-univalent electrolyte at 25°C. 

By analogy with the Helmholtz condenser formula, for small potentials the diffuse double layer can be likened to an electrical condenser of plate distance /k. For larger yo values, however, a increases more than linearly with o, and the capacity of the double layer also begins to increase. 

The Gouy-Chapman treatment of the double layer runs into difficulties at small Kx values when is large. For example, if is 300 mV, yo is 12 and if Co is, say, 10" mol/1, then the local concentration of negative ions near the surface, given by Eq. V-1, would be C = = 160 mol/1 The trouble... 

One approach to handling the double layer is to divide the region near the... 

IHP) (the Helmholtz condenser formula is used in connection with it), located at the surface of the layer of Stem adsorbed ions, and an outer Helmholtz plane (OHP), located on the plane of centers of the next layer of ions marking the beginning of the diffuse layer. These planes, marked IHP and OHP in Fig. V-3 are merely planes of average electrical property the actual local potentials, if they could be measured, must vary wildly between locations where there is an adsorbed ion and places where only water resides on the surface. For liquid surfaces, discussed in Section V-7C, the interface will not be smooth due to thermal waves (Section IV-3). Sweeney and co-workers applied gradient theory (see Chapter III) to model the electric double layer and interfacial tension of a hydrocarbon-aqueous electrolyte interface [27]. 

Charged surface plus diffuse double layer of ions —>... 

Here, the only surface adsorption is taken to be that of the charge balancing the double-layer charge, and the electrochemical potential change is equated to a change in o- Integration then gives... 

The repulsion between two double layers is important in determining the stability of colloidal particles against coagulation and in setting the thickness of a soap film (see Section VI-5B). The situation for two planar surfaces, separated by a distance 2d, is illustrated in Fig. V-4, where two versus x curves are shown along with the actual potential. 

In the preceding derivation, the repulsion between overlapping double layers has been described by an increase in the osmotic pressure between the two planes. A closely related but more general concept of the disjoining pressure was introduced by Deijaguin [30]. This is defined as the difference between the thermodynamic equilibrium state pressure applied to surfaces separated by a film and the pressure in the bulk phase with which the film is equilibrated (see section VI-5). 

A number of refinements and applications are in the literature. Corrections may be made for discreteness of charge [36] or the excluded volume of the hydrated ions [19, 37]. The effects of surface roughness on the electrical double layer have been treated by several groups [38-41] by means of perturbative expansions and numerical analysis. Several geometries have been treated, including two eccentric spheres such as found in encapsulated proteins or drugs [42], and biconcave disks with elastic membranes to model red blood cells [43]. The double-layer repulsion between two spheres has been a topic of much attention due to its importance in colloidal stability. A new numeri-... 

Fig. V-5. The repulsive force between crossed cylinders of radius R (1 cm) covered with mica and immersed in propylene carbonate solutions of tetraethylammonium bromide at the indicated concentrations. The dotted lines are from double-layer theory (From Ref. 51).

In the case of a charged particle, the total charge is not known, but if the diffuse double layer up to the plane of shear may be regarded as the equivalent of a parallel-plate condenser, one may write... 

A more detailed theory of electrophoresis is found in Refs. 9 and 58. The motion of the ions in the double layer due to the field F and due to the relative motion of the particle, cause a retardation of the electrophoretic motion that must be considered to... 

The double-layer is centered at x = r - t, and substitution into Eq. V-43 gives the double-layer velocity... 

Relaxations in the double layers between two interacting particles can retard aggregation rates and cause them to be independent of particle size [101-103]. Discrepancies between theoretical predictions and experimental observations of heterocoagulation between polymer latices, silica particles, and ceria particles [104] have promptetl Mati-jevic and co-workers to propose that the charge on these particles may not be uniformly distributed over the surface [105, 106]. Similar behavior has been seen in the heterocoagulation of cationic and anionic polymer latices [107]. 

The shape of the electrocapillary curve is easily calculated if it is assumed that the double layer acts as a condenser of constant capacity C. In this case, double integration of Eq. V-50 gives... 

Properties of the Electrical Double Layer at the Electrocapillary Maximum... 

Fig. V-12. Variation of the integral capacity of the double layer with potential for 1 N sodium sulfate , from differential capacity measurements 0, from the electrocapillary curves O, from direct measurements. (From Ref. 113.)...

The treatment may be made more detailed by supposing that the rate-determining step is actually from species O in the OHP (at potential relative to the solution) to species R similarly located. The effect is to make fi dependent on the value of 2 and hence on any changes in the electrical double layer. This type of analysis has permitted some detailed interpretations to be made of kinetic schemes for electrode reactions and also connects that subject to the general one of this chapter. 

Derive the general equation for the differential capacity of the diffuse double layer from the Gouy-Chapman equations. Make a plot of surface charge density tr versus this capacity. Show under what conditions your expressions reduce to the simple Helmholtz formula of Eq. V-17. 

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