Lateral programmable metallization cells (PMC) utilize the properties of electrodeposits grown over a solid electrolyte channel. Such devices have an active anode and an inert cathode separated by a long electrodeposit channel in a coplanar arrangement. The ability to transport large amount of metallic mass across the channel makes these devices attractive for various More-Than-Moore applications. Existing literature lacks a comprehensive study of electrodeposit growth kinetics in lateral PMCs. Moreover, the morphology of electrodeposit growth in larger, planar devices is also not understood. Despite the variety of applications, lateral PMCs are not embraced by the semiconductor industry due to incompatible materials and high operating voltages needed for such devices. In this work, a numerical model based on the basic processes in PMCs – cation drift and redox reactions – is proposed, and the effect of various materials parameters on the electrodeposit growth kinetics is reported. The morphology of the electrodeposit growth and kinetics of the electrodeposition process are also studied in devices based on Ag-Ge30Se70 materials system. It was observed that the electrodeposition process mainly consists of two regimes of growth – cation drift limited regime and mixed regime. The electrodeposition starts in cation drift limited regime at low electric fields and transitions into mixed regime as the field increases. The onset of mixed regime can be controlled by applied voltage which also affects the morphology of electrodeposit growth. The numerical model was then used to successfully predict the device kinetics and onset of mixed regime. The problem of materials incompatibility with semiconductor manufacturing was solved by proposing a novel device structure. A bilayer structure using semiconductor foundry friendly materials was suggested as a candidate for solid electrolyte. The bilayer structure consists of a low resistivity oxide shunt layer on top of a high resistivity ion carrying oxide layer. Devices using Cu2O as the low resistivity shunt on top of Cu doped WO3 oxide were fabricated. The bilayer devices provided orders of magnitude improvement in device performance in the context of operating voltage and switching time. Electrical and materials characterization revealed the structure of bilayers and the mechanism of electrodeposition in these devices.

Counterfeiting of goods is a widespread epidemic that is affecting the world economy. The conventional labeling techniques are proving inadequate to thwart determined counterfeiters equipped with sophisticated technologies. There is a growing need of a secure labeling that is easy to manufacture and analyze but extremely difficult to copy. Programmable metallization cell technology operates on a principle of controllable reduction of a metal ions to an electrodeposit in a solid electrolyte by application of bias. The nature of metallic electrodeposit is unique for each instance of growth, moreover it has a treelike, bifurcating fractal structure with high information capacity. These qualities of the electrodeposit can be exploited to use it as a physical unclonable function. The secure labels made from the electrodeposits grown in radial structure can provide enhanced authentication and protection from counterfeiting and tampering.

So far only microscale radial structures and electrodeposits have been fabricated which limits their use to labeling only high value items due to high cost associated with their fabrication and analysis. Therefore, there is a need for a simple recipe for fabrication of macroscale structure that does not need sophisticated lithography tools and cleanroom environment. Moreover, the growth kinetics and material characteristics of such macroscale electrodeposits need to be investigated. In this thesis, a recipe for fabrication of centimeter scale radial structure for growing Ag electrodeposits using simple fabrication techniques was proposed. Fractal analysis of an electrodeposit suggested information capacity of 1.27 x 1019. The kinetics of growth were investigated by electrical characterization of the full cell and only solid electrolyte at different temperatures. It was found that mass transport of ions is the rate limiting process in the growth. Materials and optical characterization techniques revealed that the subtle relief like structure and consequently distinct optical response of the electrodeposit provides an added layer of security. Thus, the enormous information capacity, ease of fabrication and simplicity of analysis make macroscale fractal electrodeposits grown in radial programmable metallization cells excellent candidates for application as physical unclonable functions.