Highly Conductive and Conformal Poly(3,4-ethylenedioxythiophene) (PEDOT) Thin Films via Oxidative Molecular Layer Deposition

Atanasov, Sarah E.; Losego, Mark D.; Gong, Bin; Sachet, Edward; Maria, Jon Paul; Williams, Philip S.; Parsons, Gregory N.

doi:10.1021/cm500825b

Cited by 96 publications

(150 citation statements)

References 35 publications

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“…300C shows no significant film growth (Figure S2). Atanasov et al reported oxidative polymerization in a molecular layer deposition process, indicating the possibility of such surface-controlled polymerization reactions 50. …”

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confidence: 99%

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

et al. 2017

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ABSTRACT:Several active areas of research in novel energy storage technologies, including threedimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tertbutoxide (LiO t Bu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2 PO 2 N between 250 and 300C. The P/N ratio of the films is always 1, indicative of a particular polymorph of LiPON which closely resembles a polyphosphazene. Films grown at 300C have an ionic conductivity of 6.51 (±0.36) × 10 −7 S/cm at 35C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li+. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2 . The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<100nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.3

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confidence: 99%

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

et al. 2017

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“…Upon spin-coating from solution, the micelles are deposited as a film and can have conductivities on the order of ∼1 S/cm (22). Subsequent annealing, treatment with cosolvents, and postprocessing steps can increase the conductivity of films to over 3,000 S/cm (23,24). High-performing spin-cast PEDOT:PSS TCs have reached a sheet resistance of 46 Ω/□ at 90% transmission (25,26).…”

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confidence: 99%

Ultrahigh electrical conductivity in solution-sheared polymeric transparent films

Worfolk

Andrews

Park

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

265

226

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With consumer electronics transitioning toward flexible products, there is a growing need for high-performance, mechanically robust, and inexpensive transparent conductors (TCs) for optoelectronic device integration. Herein, we report the scalable fabrication of highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films via solution shearing. Specific control over deposition conditions allows for tunable phase separation and preferential PEDOT backbone alignment, resulting in record-high electrical conductivities of 4,600 ± 100 S/cm while maintaining high optical transparency. High-performance solution-sheared TC PEDOT:PSS films were used as patterned electrodes in capacitive touch sensors and organic photovoltaics to demonstrate practical viability in optoelectronic applications.transparent conductor | solution shearing | PEDOT:PSS

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“…The resulting oCVD CPs properties such as conductivity can be tuned by controlling the VOCl 3 and monomer flow rates as well as the substrate temperature. Molybdenum pentachloride (MoCl 5 ) is another solid oxidant demonstrated with oxidative molecular layer deposition (oMLD) . The oMLD method is a chemical extension of atomic and molecular layer deposition and introduces the oxidant and monomer vapors sequentially into a reactor chamber .…”

Section: Ocvd Synthesis Chemistrymentioning

confidence: 99%

“…Molybdenum pentachloride (MoCl 5 ) is another solid oxidant demonstrated with oxidative molecular layer deposition (oMLD) . The oMLD method is a chemical extension of atomic and molecular layer deposition and introduces the oxidant and monomer vapors sequentially into a reactor chamber . This is in contrast to the simultaneous delivery of the oxidant and monomer vapors for the oCVD method.…”

Section: Ocvd Synthesis Chemistrymentioning

confidence: 99%

Device Fabrication Based on Oxidative Chemical Vapor Deposition (oCVD) Synthesis of Conducting Polymers and Related Conjugated Organic Materials

Gharahcheshmeh

Gleason

2018

Adv Materials Inter

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lightweight, wearable, and stretchable properties of CPs relative to traditional materials highlight the areas where CPs may find their niche in modern devices. [2] The fabrication of uniform CPs in large scale with high throughput roll-to-roll process is of great importance in industrial sectors. To achieve this purpose, chemical vapor deposition (CVD) along with other vapor deposition methods are the promising approaches to expedite the commercialization process of CPs in large-scale applications.For polymers which dissolve, films can be formed by solution-based methods such as dip-coating and spin-coating. However, CPs, particularly those formed from unfunctionalized monomers, are often insoluble or require solvents which are unsafe and costly to use. The lack of solubility is typically associated with a rigid backbone structure that promotes crystallite formation. As a result, dissolution requires overcoming the associated enthalpy of crystallization.The need for solubilizing polymers is eliminated by employing CVD as the thin film formation technique. A variety of different CVD processes have been developed for vapor phase reactants to undergo similar polymerization mechanisms as those reported for solution synthesis. [3] These include CVD polymer methods for chain growth by free radical or cationic initiation, or by condensation polymerization. For most conjugated macromolecules, the desired variant of the CVD method needs to mimic the step-growth polymerization mechanism in order to obtain optimized properties, such as electrical conductivity. This motivated the invention of oxidative CVD (oCVD) in which the vacuum chamber design, strategy for reactant vapor introduction, and process conditions are optimized for step-growth polymerization. Vapor deposition methods which are not mechanistically motivated, such as thermal evaporation, pulsed laser deposition, and plasma-enhanced CVD, can result in conjugated polymer films having properties that are insufficient for integration into many types of devices. Thus, one major significance of achieving conjugated polymers having highly desirable characteristics by oCVD is the ability to fabricate state-of-the-art optoelectronic and energy storage devices.The oCVD process is a single-step method to convert vapor phase monomers, along with vapors of oxidant, into thin CP films. [3,4] At the surface of the substrate, step-growth Conducting polymers (CPs) combine electronic conductivity, optical transparency, and mechanical flexibility compatible with lightweight substrates. Due to these features CPs exhibit promising performance for a wide range of applications including electronic, optoelectronic, electrochemical, optochemical, and energy storage and harvesting devices. Fabrication of high-quality CPs thin film in a large scale is of high demand in multiple industrial sectors. Chemical vapor deposition (CVD) is a promising approach for scale-up and commercialization of CPs in large-scale thin film applications by a roll-to-roll process. The CVD technique is a versati...

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Highly Conductive and Conformal Poly(3,4-ethylenedioxythiophene) (PEDOT) Thin Films via Oxidative Molecular Layer Deposition

Cited by 96 publications

References 35 publications

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

Ultrahigh electrical conductivity in solution-sheared polymeric transparent films

Device Fabrication Based on Oxidative Chemical Vapor Deposition (oCVD) Synthesis of Conducting Polymers and Related Conjugated Organic Materials

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