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- Genre: Doctoral Dissertation
- Creators: Goryll, Michael
- Member of: ASU Electronic Theses and Dissertations
Description
Programmable metallization cell (PMC) technology employs the mechanisms of metal ion transport in solid electrolytes (SE) and electrochemical redox reactions in order to form metallic electrodeposits. When a positive bias is applied to an anode opposite to a cathode, atoms at the anode are oxidized to ions and dissolve into the SE. Under the influence of the electric field, the ions move to the cathode and become reduced to form the electrodeposits. These electrodeposits are filamentary in nature and persistent, and since they are metallic can alter the physical characteristics of the material on which they are formed. PMCs can be used as next generation memories, radio frequency (RF) switches and physical unclonable functions (PUFs).
The morphology of the filaments is impacted by the biasing conditions. Under a relatively high applied electric field, they form as dendritic elements with a low fractal dimension (FD), whereas a low electric field leads to high FD features. Ion depletion effects in the SE due to low ion diffusivity/mobility also influences the morphology by limiting the ion supply into the growing electrodeposit.
Ion transport in SE is due to hopping transitions driven by drift and diffusion force. A physical model of ion hopping with Brownian motion has been proposed, in which the ion transitions are random when time window is larger than characteristic time. The random growth process of filaments in PMC adds entropy to the electrodeposition, which leads to random features in the dendritic patterns. Such patterns has extremely high information capacity due to the fractal nature of the electrodeposits.
In this project, lateral-growth PMCs were fabricated, whose LRS resistance is less than 10Ω, which can be used as RF switches. Also, an array of radial-growth PMCs was fabricated, on which multiple dendrites, all with different shapes, could be grown simultaneously. Those patterns can be used as secure keys in PUFs and authentication can be performed by optical scanning.
A kinetic Monte Carlo (KMC) model is developed to simulate the ion transportation in SE under electric field. The simulation results matched experimental data well that validated the ion hopping model.
The morphology of the filaments is impacted by the biasing conditions. Under a relatively high applied electric field, they form as dendritic elements with a low fractal dimension (FD), whereas a low electric field leads to high FD features. Ion depletion effects in the SE due to low ion diffusivity/mobility also influences the morphology by limiting the ion supply into the growing electrodeposit.
Ion transport in SE is due to hopping transitions driven by drift and diffusion force. A physical model of ion hopping with Brownian motion has been proposed, in which the ion transitions are random when time window is larger than characteristic time. The random growth process of filaments in PMC adds entropy to the electrodeposition, which leads to random features in the dendritic patterns. Such patterns has extremely high information capacity due to the fractal nature of the electrodeposits.
In this project, lateral-growth PMCs were fabricated, whose LRS resistance is less than 10Ω, which can be used as RF switches. Also, an array of radial-growth PMCs was fabricated, on which multiple dendrites, all with different shapes, could be grown simultaneously. Those patterns can be used as secure keys in PUFs and authentication can be performed by optical scanning.
A kinetic Monte Carlo (KMC) model is developed to simulate the ion transportation in SE under electric field. The simulation results matched experimental data well that validated the ion hopping model.
ContributorsYu, Weijie (Author) / Kozicki, Michael N (Thesis advisor) / Barnaby, Hugh (Thesis advisor) / Diaz, Rodolfo (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2015
Description
Programmable Metallization Cell (PMC) devices are, in essence, redox-based
solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices.
solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices.
ContributorsBalaban, Mehmet Bugra (Author) / Kozicki, Michael N (Thesis advisor) / Barnaby, Hugh J (Committee member) / Goryll, Michael (Committee member, Committee member) / Arizona State University (Publisher)
Created2020