Although both materials are electrically neutral, n-type silicon has excess electrons and p-type silicon has excess holes. Sandwiching these together creates a p/n junction at their interface, thereby creating an electric field.
When the p-type and n-type semiconductors are sandwiched together, the excess electrons in the n-type material flow to the p-type, and the holes thereby vacated during this process flow to the n-type. (The concept of a hole moving is somewhat like looking at a bubble in a liquid. Although it's the liquid that is actually moving, it's easier to describe the motion of the bubble as it moves in the opposite direction.) Through this electron and hole flow, the two semiconductors act as a battery, creating an electric field at the surface where they meet (known as the "junction"). It's this field that causes the electrons to jump from the semiconductor out toward the surface and make them available for the electrical circuit. At this same time, the holes move in the opposite direction, toward the positive surface, where they await incoming electrons.
