Hi,
A boot-time scan has avast check your drive(s) during the boot-up process, essentially before Windows has loaded, so you don't run into that "file is in use" problem.
If you open the "main" menu (i.e., with the inferface open, not that tooltray-icon menu), you'll see one of the choices is Schedule Boot-Time Scan. Select that, then the kind of scan you want, and it'll then tell you you'll need to reboot and do you want to do that now. Answer yes, and avast will do the scan, then reboot one more time normally.