Analytical Approach to the Local Contact Potential Difference on (001) Ionic Surfaces: Implications for Kelvin Probe Force Microscopy

TL;DR

This paper presents an analytical model for the electrostatic force in nc-AFM on ionic surfaces, explaining atomic contrast in Kelvin Probe Force Microscopy and highlighting challenges in quantitative measurements.

Contribution

It introduces a new analytical approach to model short-range electrostatic forces and the local contact potential difference on ionic surfaces in KPFM.

Findings

The electrostatic force is mainly due to tip-surface and Madelung potential interactions.

An explicit expression for the bias voltage to cancel the CPD is derived.

Quantitative KPFM measurements are complicated by tip geometry and other factors.

Abstract

An analytical model of the electrostatic force between the tip of a non-contact Atomic Force Microscope (nc-AFM) and the (001) surface of an ionic crystal is reported. The model is able to account for the atomic contrast of the local contact potential difference (CPD) observed while nc-AFM-based Kelvin Probe Force Microscopy (KPFM) experiments. With the goal in mind to put in evidence this short-range electrostatic force, the Madelung potential arising at the surface of the ionic crystal is primarily derived. The expression of the force which is deduced can be split into two major contributions: the first stands for the coupling between the microscopic structure of the tip apex and the capacitor formed between the tip, the ionic crystal and the counter-electrode; the second term depicts the influence of the Madelung surface potential on the mesoscopic part of the tip, independently from its microscopic structure. These short-range electrostatic forces are in the range of ten pico-Newtons. When explicitly considering the crystal polarization, an analytical expression of the bias voltage to be applied on the tip to compensate for the local CPD, i.e. to cancel the short-range electrostatic force, is derived. The compensated CPD has the lateral periodicity of the Madelung surface potential. However, the strong dependence on the tip geometry, the applied modulation voltage as well as the tip-sample distance, which can even lead to an overestimation of the real surface potential, makes quantitative KPFM measurements of the local CPD extremely difficult.