In semiconductor electrochemistry, a Mott–Schottky plot describes the reciprocal of the square of capacitance ( 1 / C 2 ) {\displaystyle (1/C^{2})} versus the potential difference between bulk semiconductor and bulk electrolyte. In many theories, and in many experimental measurements, the plot is linear. The use of Mott–Schottky plots to determine system properties (such as flatband potential, doping density or Helmholtz capacitance) is termed Mott–Schottky analysis.
Consider the semiconductor/electrolyte junction shown in Figure 1. Under applied bias voltage V {\displaystyle V} the size of the depletion layer w {\displaystyle w} is
w = [ 2 ε q N D ( V + V bi ) ] 1 / 2 {\displaystyle w={\left\lbrack {\frac {2\varepsilon }{{\mathit {q}}{\mathit {N}}_{D}}}\left(V+{V}_{\text{bi}}\right)\right\rbrack }^{1/2}} (1) Here ε = ε r ε 0 {\displaystyle \varepsilon =\varepsilon _{r}\varepsilon _{0}} is the permittivity, q {\displaystyle q} is the elementary charge, N D {\displaystyle {N}_{D}} is the doping density, V bi {\displaystyle {V}_{\text{bi}}} is the built-in potential. The depletion region contains positive charge compensated by ionic negative charge at the semiconductor surface (in the liquid electrolyte side). Charge separation forms a dielectric capacitor at the interface of the metal/semiconductor contact. We calculate the capacitance for an electrode area A {\displaystyle A} as
C = ∂ Q ∂ V = q N D A ∂ w ∂ V {\displaystyle C={\frac {\partial Q}{\partial V}}={\mathit {q}}{\mathit {N}}_{D}A{\frac {\partial w}{\partial V}}} (2) replacing ∂ w ∂ V {\displaystyle {\frac {\partial w}{\partial V}}} as obtained from equation 1, the result of the capacitance per unit area is
C = A ε w {\displaystyle C=A{\frac {\varepsilon }{w}}} (3) a equation describing the capacitance of a capacitor constructed of two parallel plates both of area A {\displaystyle A} separated by a distance w {\displaystyle w} . Replacing equation (3) in (1) we obtain the result
C − 2 = 2 q A 2 ε N D ( V + V bi ) {\displaystyle {C}^{-2}={\frac {2}{{\mathit {qA}}^{2}{\mathit {\varepsilon N}}_{D}}}\left(V+{V}_{\text{bi}}\right)} (4). Therefore, a representation of the reciprocal square capacitance, is a linear function of the voltage, which constitutes the Mott–Schottky plot as shown in Fig. 1c. The measurement of the Mott–Schottky plot brings us two important pieces of information.
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![Mott–Schottky plot: Figure 1. (a) Shows an energy diagram of n-type semiconductor in contact with redox electrolyte at the left side (yellow), and with a metallic ohmic contact at the right side. Ec is the conduction band edge energy, Ev is the valence band energy of the semiconductor. By equilibration of the Fermi level in the semiconductor, EF, and the redox energy of electrolyte, Eredox, a Schottky barrier is formed at the semiconductor/electrolyte interface. The vertical size of the barrier in the energy diagram corresponds to the built-in potential Vbi. In the spatial axis the equilibration of Fermi levels produces a space charge region or depletion region of size w. A positive voltage applied to the back contact in (b) raises the Fermi level of electrons EFn, and decreases the size of the depletion region. Consequently, the capacitance of the junction increases, and the reciprocal square capacitance decreases forming a linear Mott–Schottky plot in (c). The intercept with the x-axis shows the flatband situation, that reveals the built-in potential, depending on the reference of voltage in the electrolyte side. (d) In the presence of a surface state of density Nss, when the Fermi level reaches the bandgap state level, it is discharged and a plateau occurs depending on the value of the Helmholtz layer capacitance CH at the electrolyte side of the junction. When the surface state is charged the Mott–Schottky lines continues, but the flatband potential is modified according to the extent of unpinning of the Fermi level. Adapted from[1]](https://upload.wikimedia.org/wikipedia/commons/thumb/0/04/Mott-Schottky_plot_scheme.tif/lossless-page1-1280px-Mott-Schottky_plot_scheme.tif.png?utm_source=en.wikipedia.org&utm_campaign=parser&utm_content=thumbnail)

