In this work As doped polysilicon was deposited onto (100) silicon wafers by APCVD at 660°C from a silane-arsine mixture, followed by a ten minute anneal at 1000°C, and in one case a further ten minute anneal at 700°C. Specimens for TEM and STEM analysis were prepared by chemical polishing. The microstructure, which is unchanged by the final 700°C anneal,is shown in Figure 1. It consists of numerous randomly oriented grains many of which contain twins.X-ray analysis was carried out in a VG HB5 STEM. As K α x-ray counts were collected from STEM scans across grain and twin boundaries, Figures 2-4. The incident beam size was about 1.5nm in diameter, and each of the 20 channels in the plots was sampled from a 1.6nm length of the approximately 30nm line scan across the boundary. The bright field image profile along the scanned line was monitored during the analysis to allow correlation between the image and the x-ray signal.