Routes to 3D conformal solid-state dielectric polymers: electrodeposition versus initiated chemical vapor deposition

Abstract

We show that two distinct methods, electropolymerization and initiated chemical vapour deposition (iCVD), can be adapted to generate ultrathin polymers (30-50 nm thick) at three dimensionally (3D) porous conductive substrates comprising B300 lm-thick carboncoated silica fiber paper (C@SiO 2 ). We selected 1,3,5-trivinyl-1,3,5trimethylcyclotrisiloxane (''V3D3'') as a common monomer amenable to polymerization by either approach. Electroanalytical and electrical measurements confirm that all carbon surfaces are passivated with electronically insulating poly(V3D3) coatings.The Achilles heel that trips up all-solid-state 3D energy-storage devices resides in the inability to form ultrathin dielectrics with high fidelity when conformally coating non-line-of-sight substrates such as ultraporous scaffolds and architectures. Of the limited fabrication protocols available to paint polymers throughout macroscopically thick structures while ''blind,'' electrodeposition and initiated chemical vapour deposition are the most compelling. Both methods offer conditions under which growth can be limited thus ensuring that monomer can access all of the internal surfaces. The critical chemical, physical, and electrical properties of nanoscale polymers generated by such methods-well-studied on planar substrates-must also be validated for the polymers when expressed in 3D. These data are necessary to demonstrate performance as a solid-state dielectric in 3D batteries and capacitors.

One-step vapor-phase synthesis of transparent high refractive index sulfur-containing polymers

“…The SCPs from allyl compounds, poly(sulfur-co-1,11-dodecadiene) (SDDDE) and poly(sulfur-co-1,9-decadiene) (SDDE), also showed characteristic peaks around 2900 cm −1 , representing the C─H stretching. Analogously in the FTIR spectra of polymers with organosilicon-containing monomers including 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4), and hexavinyldisiloxane (HVDS), the peak at 1260 cm −1 corresponding to the Si─C bond is observed (27,28), confirming the full retention of the characteristic functional groups of each monomer, regardless of the monomer species. All the SCPs prepared by sCVD had not been reported to date by other synthesis method to date, which strongly suggest that a wide variety of SCPs can further be generated directly from elemental sulfur through sCVD in expanded manner, The results also demonstrate that this unique sulfur copolymerization method is a versatile platform for the preparation of high-sulfur content polymer thin films with tailored molecular structure and functions.…”

Pyrolytic Carbon Films with Tunable Electronic Structure and Surface Functionality: A Planar Stand‐In for Electroanalysis of Energy‐Relevant Reactions

“…The pyC films were prepared similarly to those previously reported. [25,45,52] Briefly, pre-cleaned quartz slides were placed on an alumina crucible plate within a tube furnace (Thermo Scientific Lindberg Blue M). The temperature was ramped to 1000°C under flowing Ar at a rate of 10°C min À 1 .…”

CVD Polymers for Devices and Device Fabrication

“…2017, 29,1604606 www.advancedsciencenews.com www.advmat.de Figure 3. a) Schematic of crystalline PFDA domains with MAA proton conduction channels; [58] b) top: thermal shrinkage of PE separators with and without iCVD coatings, bottom: water contact angle on separator with and without iCVD coatings; [64] c) SEM cross section of conformal iCVD pV3D3 coated on C@SiO 2 fiber; [53] d) DFT simulation of V4D4 monomer electron densities. Blue volumes indicate areas of negative charge; [80] e) False color TEM of iCVD pV4D4 on spinel particle supplied by Veronica Augustyn of the Manthiram group at the University of Texas-Austin.…”

“…c) Reproduced with permission. [53] Copyright 2015, Royal Society of Chemistry. d) Reproduced with permission.…”

“…Rolison and co-workers compared the electropolymerization (EP) and iCVD synthesis of pV3D3, an analogue of pV4D4 with a smaller ring structure. [53] In this study, 30-50 nm thick pV3D3-synthesized through both routes was deposited on carbon coated silica (C@SiO 2 ) fiber paper. The underlying fiber structure was best retained with the iCVD method, as seen in the SEM cross section in Figure 3c.…”