Compound semiconductor devices and methods of doping compound semiconductors are provided. Embodiments of the invention provide post-deposition (or post-growth) doping of compound semiconductors, enabling nanoscale compound semiconductor devices including diodes and transistors. In one method, a self-limiting monolayer technique with an annealing step is used to form shallow junctions. By forming a sulfur monolayer on a surface of an InAs substrate and performing a thermal annealing to drive the sulfur into the InAs substrate, n-type doping for InAs-based devices can be achieved. The monolayer can be formed by surface chemistry reactions or a gas phase deposition of the dopant. In another method, a gas-phase technique with surface diffusion is used to form doped regions. By performing gas-phase surface diffusion of Zn into InAs, p-type doping for InAs-based devices can be achieved. Both bulk and nanowire devices using compound semiconductors can be fabricated using these surface and gas-phase doping processes.