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Make sure that the background is lit brighter than the subject, and expose for the background. If you can backlight the subject, sometimes you'll get a nice effect. A person in front of a window will usually come out silhouetted whether you want it or not. A silhouette really is just underexposure of the subject relative to something else which is exposed brightly. The greater the dynamic contrast between subject and background, the better the silhouette.
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