title: Atomic Resolution of Calcium and Oxygen Sublattices of Calcite in Ambient Conditions by Atomic Force Microscopy Using qPlus Sensors with Sapphire Tips.
abstract: Characterization and imaging at the atomic scale with atomic force microscopy in biocompatible environments is an ongoing challenge. We demonstrate atomically resolved imaging of the calcite (101̅4) surface plane using stiff quartz cantilevers ("qPlus sensors", stiffness k = 1280 N/m) equipped with sapphire tips in ambient conditions without any surface preparation. With 10 atoms in one surface unit cell, calcite has a highly complex surface structure comprising three different chemical elements (Ca, C, and O). We obtain true atomic resolution of calcite in air at relative humidity ranging from 20% to 40%, imaging atomic steps and single atomic defects. We observe a great durability of sapphire tips with their Mohs hardness of 9, only one step below diamond. Depending on the state of the sapphire tip, we resolve either the calcium or the oxygen sublattice. We determine the tip termination by comparing the experimental images with simulations and discuss the possibility of chemical tip identification in air. The main challenges for imaging arise from the presence of water layers, which form on almost all surfaces and have the potential to dissolve the crystal surface. Frequency shift versus distance spectra show the presence of at least three ordered hydration layers. The measured height of the first hydration layer corresponds well to X-ray diffraction data and molecular dynamic simulations, namely, ∼220 pm. For the following hydration layers we measure ∼380 pm for the second and third layer, ending up in a total hydration layer thickness of at least 1 nm. Understanding the influence of water layers and their structure is important for surface segregation, surface reactions including reconstructions, healing of defects, and corrosion.
authors: Institute of Experimental and Applied Physics, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany.
authors: Daniel S
authors: DS
authors: Wastl
authors: Institute of Experimental and Applied Physics, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany.
authors: Michael
authors: M
authors: Judmann
authors: Institute of Experimental and Applied Physics, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany.
authors: Alfred J
authors: AJ
authors: Weymouth
authors: Institute of Experimental and Applied Physics, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany.
authors: Franz J
authors: FJ
authors: Giessibl
mesh_terms: D000537:Aluminum Oxide; D002118:Calcium / Q000737:chemistry*; D002119:Calcium Carbonate / Q000737:chemistry*; D018625:Microscopy, Atomic Force / Q000295:instrumentation*; D057054:Molecular Imaging; D010100:Oxygen / Q000737:chemistry*
chemical_list: D002119:Calcium Carbonate; D000537:Aluminum Oxide; D010100:Oxygen; D002118:Calcium
keywords: ambient conditions; atomic force microscopy (AFM); atomic resolution; calcite; qPlus