Once you have launched the Layer Window, you can click on the Brush Tool in the Tools Palette. Open Auto Palettes is handy to have checked as it automatically opens the Paint Palette and the Brush Tips Palette. Otherwise you can click the palette icon.
If you prefer to use the keyboard to select tools, press Cmd+B (Crtl+B). Keep pressing Cmd+B (Crtl+B)to toggle between the Paint, Clone, and Erase Tools. If you are using the keyboard shortcuts because you lack monitor real estate, double-clicking on any palette will collapse it and save you room.