Surface morphology, chemical contrast, and ferroelectric domains in TGS bulk single crystals differentiated with UHV non-contact force microscopy

Ferroelectric bulk single crystals of tri-glycine sulphate (TGS) have been investigated in ultra-high vacuum (UHV) using dynamic force microscopy (DFM) in the non-contact (nc) mode. Both chemical contrast from different sub-unit cell cleavage steps, and ferroelectric domains were differentiated by recording the variation in interaction force affecting the excitation amplitude A_exc applied to the piezo shaker in constant amplitude DFM. No chemical difference was found for steps measuring half the unit cell height b, in contrast to b/4—steps where sulphate ions change the local short-range chemical forces. By varying the bias voltage applied to the TGS counter electrode, the sign of bound surface charge within each ferroelectric domain was determined. Domain walls separating regions with antiparallel polarisation vectors are resolved down to a 9 nm domain wall width. Furthermore, we achieved atomic resolution with nc-DFM on cleaved TGS samples indicating the monoclinic unit cell at the ferroelectric sample surface with a=1.0±0.05 nm, c=0.55±0.05 nm, and β=107±3°.