Atomic resolution transmission electron microscopy visualisation of channel occupancy in beryl in different crystallographic directions

Abstract

The causes of colour in beryl have been a research topic for decades. For some varieties, such as emerald (green, coloured by Cr³⁺ and/or V³⁺), the main cause of colour is substitutions by metal atoms within the framework. However, the causes for the yellow and blue colours in heliodor, golden beryl and aquamarine are still debated. It is generally agreed that Fe ions are responsible for the colour, but there are differing conclusions about the valence states of these ions, the occupied positions and the colour-inducing processes involved. The colour of aquamarine is commonly attributed to intervalence charge transfer (IVCT) between Fe³⁺ and Fe²⁺. Various combinations of sites have been proposed to host the Fe ions engaging in this IVCT. Here we present a new approach to address the topic of colour generation: atomic resolution scanning transmission electron microscopy (STEM). For the first time, atomic resolution images of a beryl (natural aquamarine) are presented in the three crystallographic directions [0001], [1-210] and [1-100]. Ions are clearly resolved in the channels. From the ratio of channel occupation and the correlation of the atoms per formula unit (apfu) calculations we conclude that Fe resides in the framework, not in the channels. The projections in the [1-210] direction directly show that the cavity channel site 2a is occupied, most likely by Cs, in agreement with recent results in the literature.