Solid solutions of metals such as silver in arsenic trisulfide exhibit a variety of interesting characteristics, including the ability to bring the metal out of solution by electrodeposition. This allows voltage-controlled switching characteristics to be realized in two terminal devices which may be fabricated to nanoscale dimensions. In addition, surface electrodeposits may be formed and subsequently broken at grain boundaries to create structures that have adjustable current–voltage characteristics at low temperatures. This paper highlights some initial results of the characterization of nanoscale structures based on such solid solutions.