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Although the refractive index of the adsorbate film is certainly a function of coverage, it is not directly determinable for submonolayer films and is, therefore, commonly assumed to be constant and equal to the value of a full monolayer, which means that any changes in the ellipsometric angles Δ and Ψ are interpreted as changes in film thickness. The error introduced by this assumption has been shown (see ref 7) to be small (<1 Å) for hydrocarbon films undergoing a transition from a liquidlike structure (n ≈ 1.43) at low coverage to a crystalline, densely packed structure (n ≈ 1.50) at high coverage (continuous film growth). For an island-type growth mechanism, on the other hand, the (macroscopic) film refractive index is expected to change more drastically between n = 1 (uncovered surface in contact with air) and 1.50 (full monolayer), see ref 22. Whereas the true film thickness (i.e., the height of the islands) is independent of coverage in this case, the ellipsometrically measured values for an assumed constant refractive index represent the weighted average of covered and uncovered surface regions and, therefore, reflect the changes in film density rather than changes in film thickness.
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