On voidites: a high-resolution transmission electron microscopic study of faceted void-like defects in natural diamonds

Abstract

In natural diamonds of optical classification type la , nitrogen is the major identified impurity and is distributed mainly in point defects known as A defects (probably a pair of nitrogen atoms substituting for a pair of adjacent carbon atoms) and B defects (probably four substituted nitrogen atoms tetrahedrally surrounding a carbon vacancy), and also in the electron-microscopically visible platelet precipitates on {100}. This paper is concerned with other electron-microscopically detectable defects, discovered by R. F. Stephenson (Ph.D. thesis, University of Reading (1977)), that lie in {100} planes in circumstances strongly suggesting that they result from the decomposition of platelets. High-resolution electron microscopy shows these defects to be {111}-faceted cavities. They behave as pure phase-contrast objects whose interior density does not exceed about one-third that of the diamond matrix: we call them ‘voidites’. The experimental background to voidite observation is reviewed, including electron-microscopic measurements on normal {100} platelets and models of their structure, and the optical, X-ray diffraction and cathodoluminescence evidence for unusually large platelets whose presence, together with a relative richness in B defects, indicates an environment in which voidites are likely to be discovered. Almost all observed voidites are confined to sheets strictly parallel to {100}. Some voidite sheets occur in ‘ partial platelets’, where they replace part of the original area of normal platelet. Other voidite sheets occur within dislocation loops whose size and shape are similar to those of the peripheries of normal platelets in the specimen. Voidites occur in a wide range of sizes. The largest equiaxed voidites observed measure about 10 nm between opposite {111} facets, and the smallest resolved about 0.5 nm. Many voidites are elongated in one of the <110> directions in the plane of the voidite sheet: the most highly elongated voidites seen approach 100 nm in length, with diameters of a few nanometres. Variations in size, shape and number density of voidites, together with many other characteristics relevant to the microscopic processes of voidite formation, are discussed in detailed descriptions of about 40 voidite sheets occurring in partial platelets and dislocation loops in two diamond specimens. One specimen was free from both grown-in dislocations and dislocations associated with plastic deformation. It contained zones of highly elongated platelets and it appeared that transformation of a platelet into a voidite sheet surrounded by a dislocation loop was triggered by the mutual very close approach of platelets. The second voidite-containing specimen had suffered plastic deformation at some stage in its history, but did not exhibit direct evidence that glide dislocations had triggered the transformation. The Burgers vectors of 24 dislocation loops enclosing voidite sheets in the second specimen were determined. Twelve were of normal ½<110> type having a component ½a 0 normal to the voidite sheet, and twelve were non-primitive, the Burgers vector being a 0 normal to the voidite sheet (a 0 is the diamond face-centred cubic (fcc) unit cell edge). The volumes of over 2000 individual voidites, representing all or major parts of 12 voidite sheets, have been measured. Values found for the ratio ∑ V /Aa 0 (where ∑ V is the aggregate voidite volume in a sheet area A ) averaged about unity for 9 sheets of generally similar, voidite-rich appearance. Other sheets are poorer in voidites of measurable dimensions: the ratios for two such sheets averaged 0.25. In the concluding analysis, a reaction involving A and B point defects is proposed for the production of platelets. Other reactions including voidites (but no dislocations) are suggested in which both platelet production and elimination might occur. For the dominating reaction, when a platelet is replaced by a voidite sheet surrounded by an interstitial dislocation loop, models are developed for the cases when the Burgers vector component perpendicular to the loop is either a 0 or ½ a 0 , with the assumption that the platelet nitrogen is dispersed partly into B defects and partly into the voidites. The predicted values of ∑ V /Aa 0 come out as about unity and as 0.25 (or lower) for the larger and smaller Burgers vectors, respectively.