Stein's method is a powerful (and elegant) technique for deriving bounds on the distance between two probability distributions with respect to a probability metric. Such bounds are of interest, for example, in statistical inference when samples sizes are small; indeed, obtaining bounds on the rate of convergence of the central limit theorem was one of the most important problems in probability theory in the first half of the 20th century.
The method is based on differential or difference equations that in a sense characterise the limit distribution and coupling techniques that allow one to derive approximations whilst retaining the probabilistic intuition. There is an active area of research concerning the development of Stein's method as a probabilistic tool and its application in areas as diverse as random graph theory, statistical mechanics and queuing theory.
There is an excellent survey of Stein's method (see below) and, given a strong background in probability, the basic method can be learnt quite quickly, so it would be possible for the interested student to make progress on new problems relatively shortly into their PhD. Possible directions for research (although not limited) include: extend Stein's method to new limit distributions; generalisations of the central limit theorem; investigate `faster than would be expected' convergence rates and establish necessary and sufficient conditions under which they occur; applications of Stein's method to problems from, for example, statistical inference.
Ross, N. Fundamentals of Stein's method. Probability Surveys 8 (2011), pp. 210-293.