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Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly attractive for these applications to enable faster charging. Recent work has demonstrated that nanoscale thin films of PEDOT can be formed using sequential gas-phase exposures via oxidative molecular layer deposition, or oMLD, which provides advantages in conformality and uniformity on high aspect ratio substrates over other deposition techniques. But to date, the electrochemical properties of these oMLD PEDOT thin films have not been well-characterized. In this work, we examine the electrochemical properties of 5–100 nm thick PEDOT films formed using 20–175 oMLD deposition cycles. We find that film thickness of oMLD PEDOT films affects the orientation of ordered domains leading to a substantial change in charge storage capacity. Interestingly, we observe a minimum in charge storage capacity for an oMLD PEDOT film thickness of ∼30 nm (60 oMLD cycles at 150 °C), coinciding with the highest degree of face-on oriented PEDOT domains as measured using grazing incidence wide angle X-ray scattering (GIWAXS). Thinner and thicker oMLD PEDOT films exhibit higher fractions of oblique (off-angle) orientations and corresponding increases in charge capacity of up to 120 mA h g −1 . Electrochemical measurements suggest that higher charge capacity in films with mixed domain orientation arise from the facile transport of ions from the liquid electrolyte into the PEDOT layer. Greater exposure of the electrolyte to PEDOT domain edges is posited to facilitate faster ion transport in these mixed domain films. These insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment.
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In situ spectroscopic ellipsometry and rigorous coupled wave analysis for real time profile evolution of atomic layer deposited films inside SiO 2 nanotrenches
Rigorous coupled wave analysis (RCWA) is conducted on in situ spectroscopic ellipsometry data to understand profile evolution during film deposition inside nanotrenches. Lithographically patterned SiO 2 nanotrenches are used as test structures. The nanotrenches are 170 nm wide at the top with a taper angle of 4.5° and are 300 nm in depth. Atomic layer deposition of ZnO is used as a model process where the thickness (cycles) of the film is varied from 0 (0 cycles) to 46 nm (300 cycles). The analysis predicts transient behavior in deposition affecting film conformality and changes to the trench taper angle. In the process, the aspect ratio varies from 2.05 at the start of the process to 6.67 at the end. The model predicts changes in the refractive index of the ZnO film as a function of thickness. The real and imaginary parts of the refractive index at a wavelength of 350 nm change from 1.81 to 2.37 and 0.25 to 0.87, respectively. Scanning electron microscopy cross sections confirm thickness at the top and bottom of the trench to within 13% of those predicted by RCWA. The experimentally measured conformality degrades as film deposition proceeds from 97.3% at 100 cycles to 91.1% at 300 cycles. These results demonstrate the potential of using RCWA for continuous and in situ monitoring of growth inside 3D nanostructures.
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- Award ID(s):
- 1908167
- PAR ID:
- 10436342
- Date Published:
- Journal Name:
- Journal of Vacuum Science & Technology A
- Volume:
- 40
- Issue:
- 6
- ISSN:
- 0734-2101
- Page Range / eLocation ID:
- 062403
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1116/6.0001937
