Image Credit: Radio-Electronics.com
Phototransistors are made of semi-conductive materials. Although germanium has more desirable electrical properties, silicon is more commonly used because of its reliability and low cost.
How Phototransistors Work
A typical transistor consists of a collector, emitter, and base sections. The collector is biased positively with respect to the emitter and the base-collector junction is reverse biased. A phototransistor remains inactive until light falls onto the base. Light activates the phototransistor, allowing the formation of hole-electron pairs and the flow of current across the collector or emitter. As the current spreads it is concentrated and converted into voltage.
See example at 1:30. Video Credit: techtrainingonline
A phototransistor usually does not have a base connection (see diagram below). The base is left disconnected because the light is used to enable the current to flow through the phototransistor.