Restricted accessMoreSectionsView PDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareShare onFacebookTwitterLinked InRedditEmail Cite this article Price R., Ester G. R. and Halfpenny P. J. 1999Supersaturation-dependent polygonization of growth spirals during crystallization from solution investigated using atomic force microscopyProc. R. Soc. Lond. A.4554117–4130http://doi.org/10.1098/rspa.1999.0493SectionRestricted accessSupersaturation-dependent polygonization of growth spirals during crystallization from solution investigated using atomic force microscopy R. Price R. Price Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author , G. R. Ester G. R. Ester Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author and P. J. Halfpenny P. J. Halfpenny Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author R. Price R. Price Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author , G. R. Ester G. R. Ester Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author and P. J. Halfpenny P. J. Halfpenny Department of Materials Science and Engineering, University of Bath, Bath BA2 7AY, UK Google Scholar Find this author on PubMed Search for more papers by this author Published:08 November 1999https://doi.org/10.1098/rspa.1999.0493AbstractThe form and spacing of single–growth spirals on the {010} faces of crystals of potassium hydrogen phthalate (KAP) grown from aqueous solution have been examined using ex situ atomic force microscopy. The height of all steps observed in this study was found to be 1.4 ± 0.2 nm, which corresponds to the height of a single unit cell in the b crystallographic direction. At low supersaturation (σ = 0.015) spirals exhibited three distinct types of step, one close to [001] and two parallel to sets of (101) directions which are non–equivalent due to the point group symmetry of the KAP structure. The observation of step orientations close to [001] was unexpected since this direction is not parallel to a strong periodic bond chain. The possibility that occurrence of such steps may be due to impurity effects is discussed. Either preferential retardation of steps close to this orientation or, possibly, anisotropic kink integration of impurities on the (101) steps may be responsible. The step spacing of the two sets of (101) steps differed greatly. The spacing of all steps decreased with supersaturation, giving an approximately linear dependence of slope, p, on ln(1+σ) up to a supersaturation of around 0.03. The step edge free energies for the two (101) step orientations were estimated to be 4 and 50 mJ m–2. Above a supersaturation of approximately 0.03 a large deviation from linear dependence was observed, the origin of which is unclear. In addition to the expected change in step spacing, the spiral shape was also found to change substantially with increasing supersaturation. All step orientations became progressively more rounded with increasing supersaturation, though the extent to which this occurred differed for each non–equivalent step orientation. The greatest degree of rounding occurred for orientations close to [001], while the narrowly spaced (101) steps showed only slight rounding. Potential mechanisms for these changes are discussed and confronted with experimental observations from crystals grown in nominally pure solutions and in the presence of intentional impurities. It is concluded that surface diffusion plays a key role in the process and that step roughening occurs with increasing supersaturation, leading to a change in the ratio of mean surface diffusion distance to interkink spacing. This results in a decrease in spiral polygonization as the supersaturation is raised. 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Cubillas P, Anderson M and Attfield M (2012) Crystal Growth Mechanisms and Morphological Control of the Prototypical Metal-Organic Framework MOF-5 Revealed by Atomic Force Microscopy, Chemistry - A European Journal, 10.1002/chem.201202261, 18:48, (15406-15415), Online publication date: 26-Nov-2012. van den Bruele F, Marks K, Harmsen B, Alfring A, Sprong H, van Enckevort W and Vlieg E (2012) Surface Degradation during Separation of Crystals from Solution: Minimizing the Shut-off Effect, Crystal Growth & Design, 10.1021/cg201506y, 12:5, (2265-2271), Online publication date: 2-May-2012. Sizemore J and Doherty M (2010) A stochastic model for the critical length of a spiral edge, Journal of Crystal Growth, 10.1016/j.jcrysgro.2009.11.034, 312:6, (785-792), Online publication date: 1-Mar-2010. Barbon A, Bott E, Brustolon M, Fabris M, Kahr B, Kaminsky W, Reid P, Wong S, Wustholz K and Zanré R (2009) Triplet States of the Nonlinear Optical Chromophore DCM in Single Crystals of Potassium Hydrogen Phthalate and Their Relationship to Single-Molecule Dark States, Journal of the American Chemical Society, 10.1021/ja903284y, 131:32, (11548-11557), Online publication date: 19-Aug-2009. Sizemore J and Doherty M (2009) A New Model for the Effect of Molecular Imposters on the Shape of Faceted Molecular Crystals, Crystal Growth & Design, 10.1021/cg8011124, 9:6, (2637-2645), Online publication date: 3-Jun-2009. Panina N, Meekes H, van Enckevort W, Deroover G and Vlieg E (2009) Analysis of Growth Spirals on Vapor-Grown Metal-free β-Phthalocyanine Crystals, Crystal Growth & Design, 10.1021/cg801306j, 9:5, (2409-2414), Online publication date: 6-May-2009. McLoughlin M, Mays T and Price R (2005) Growth Spiral Activity and Step Velocities on a Crystal Surface, Physical Review Letters, 10.1103/PhysRevLett.95.115504, 95:11 Rashkovich L, Petrova E, Shustin O and Chernevich T (2003) Formation of a dislocation spiral on the (010) face of a potassium hydrogen phthalate crystal, Physics of the Solid State, 10.1134/1.1553550, 45:2, (400-407), Online publication date: 1-Feb-2003. De Yoreo J, Orme C and Land T (2001) Using atomic force microscopy to investigate solution crystal growth Advances in Crystal Growth Research, 10.1016/B978-044450747-1/50048-X, (361-380), . This Issue08 November 1999Volume 455Issue 1991 Article InformationDOI:https://doi.org/10.1098/rspa.1999.0493Published by:Royal SocietyPrint ISSN:1364-5021Online ISSN:1471-2946History: Published online08/11/1999Published in print08/11/1999 License: Citations and impact Keywordspolygonizationatomic force microscopycrystal growthspiral