Figure 2: Incorporation of carboxylated micelles and associated cavity generation.

(a–c) Sequential in situ 3 × 3 μm AFM images of growing calcite surface at σ=1.49. Particles indicated by arrows in (a) subsequently show a decrease in height (b), before undergoing complete burial (c). The inset in c shows one step (1) that has just reached a micelle, one (2) that has just closed around it and another (3) that has nearly recovered to a straight morphology with little overall inhibition. The times (t) at which the bottom and top of the images were collected are given in lower and upper right corners of images, respectively, where the bottom of (a) was arbitrarily set to t=0 s. The copolymer concentration was (a,b) 127 nM and (c) zero. (d–h) Detailed view of the incorporation of a large micelle (σ=2.66). (d; 0 s) An ellipsoidal micelle with a height of 19.6 nm and in-plane diameters of 93 nm is adsorbed to an acute step (see Supplementary Fig. 5f for determination of true micelle diameter). (e; 34 s) As incorporation proceeds, the micelle decreases in height (13.3 nm) and its shape evolves to that of an ellipsoid with a circular cross-section and reduced diameter of 84 nm. (f; 2 min 35 s) Upon further burial, a gap (blue arrow) forms around the micelle with the diameter further reduced to 33 nm (height: 0.8 nm). (g; 3 min 10 s) The cavity remains (blue arrow) after complete micelle burial before eventually closing over, (h; 31 min 58 s). (i) Calcite surface with adsorbed micelles (green arrows) in micelle-containing solution at (near-) equilibrium (step speed=0, copolymer concentration: 69 nM). (j) Upon introduction of highly supersaturated solution (σ=2.66) and consequent step advancement, many micelles (green arrows) appear because of increased capture rate by steps. Many have already become incorporated and formed cavities (blue arrow). (k) Reappearance of incorporated micelles in etchpits upon dissolution. Scale bars; (a) 750 nm, (d, inset to c) 100 nm and (i–k) 300 nm. Images a–h and i–k were collected in contact and tapping mode, respectively.