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Flash
When setting up your camera for a silhouette, make sure your camera's flash is turned off. You don't want to add any light from the camera side, which will brighten your subject and ruin the silhouette effect. You can add more light from behind your subject using an off-camera flash. Set-up for a remote flash system varies from camera to camera and flash to flash. Consult your user manual for specific instructions.
Shutter Speed
Shoot the picture at the fastest shutter speed available to ensure that your subject is under-exposed. This will create a rich black shadow. If you don't like the resulting image that shows up in your preview screen, slow down the shutter speed to add more color and pop to the background. But be careful. Slowing down the shutter speed too much will also lighten your subject and allow you to start seeing more detail and features.
Aperture
The aperture, or f/stop, controls the amount of light coming through the lens and the depth of field of a picture. The larger the aperture, the more light used and the sharper the background will be. Shallow depth of field is important to portrait photography, but not very effective with silhouettes. Because your subject is a dark outline, you want to see the background in sharp focus. This means choosing the largest aperture, or f/stop, available.
Shooting Modes
You need to shoot in full manual mode to control the shutter speed and aperture settings. But many compact digital cameras don't have a manual mode. If this is the case, first look for a shutter-priority mode, often marked by "Tv." This will allow you to choose the shutter speed, while the camera sets the aperture. If you're not happy with the way the background looks, try taking the picture in aperture priority mode, or "Av." If you don't have either of those options, try selecting "landscape" or a similar option. This mode is preprogrammed to use a high aperture setting.