Theoretical evaluation of the effective work functions for positive-ionic and electronic emissions from polycrystalline metal surfaces

Effective work functions (φ⁺ and φ^e) for positive-ionic and electronic emissions from polycrystalline metals of Nb, Mo, Ta, W and Ir are calculated according to our theoretical model by using those published data on both fractional surface area (F_i) and local work function (φ_i) of each metal surface composed of several patchy faces (1, 2, …, i). Comparison between the theoretical values thus obtained and those experimental data published to date yields the conclusions as follows. (1) With a slight error of less than ∼0.1 eV, the value of φ^e calculated with each of the metals is in fair or good agreement with that determined by experiment. (2) Such agreement is found also with φ⁺ for W. (3) In a typical case of W, where the degree of monocrystallization (δ_m) corresponding to the largest among the values of F_i is less than ∼0.5, the thermionic contrast (Δφ* ≡ φ⁺ − φ^e) is found again to be nearly equal to both theoretical and experimental values reported previously. (4) Each of the five metals shows that Δφ* at δ_m = 0.68-0.95 is smaller than Δφ* at δ_m < 0.5. (5) This result strongly supports our theoretical prediction that Δφ* decreases gradually to zero as δ_m increases beyond ∼0.5 up to ∼1. (6) Particularly, such a surface which has δ_m ≥ 0.96 exhibits Δφ* ≈ 0, apparently equivalent to the so-called “monocrystalline surface (δ_m = 1)”. These results lead to the conclusion that our theoretical model is valid for evaluating the effective work functions probably with a slight error of less than ∼0.1 eV, irrespective of both the surface species and the range of δ_m. In addition, our simple model makes it possible to analyze the mechanism of change in φ⁺ and φ^e according to the change in surface characters of both φ_i and F_i.