Efficient Charge Transport in Assemblies of Surfactant‐Stabilized Semiconducting Nanoparticles

Bag, Monojit; Gehan, Timothy S.; Algaier, Dana D.; Liu, Feng; Gavvalapalli, Nagarjuna; Lahti, Paul M.; Russell, Thomas P.; Venkataraman, D.

doi:10.1002/adma.201301302

Cited by 43 publications

(43 citation statements)

References 27 publications

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“…More importantly, nanoparticle–nanoparticle contacts do not act as high energy interfaces observed in inorganic systems. This finding is consistent with electronic transport measurements of P3HT nanoparticle assemblies that show comparable transport properties to bulk P3HT films, and now confirmed for ionic transport.…”

Section: Resultssupporting

confidence: 87%

“…Surfactant stabilized polymer nanoparticles were fabricated via a previously reported method of postpolymerization miniemulsion, which is detailed in the Experimental Section. It has been previously shown that surfactants used in nanoparticle synthesis do not dope P3HT, which is not easily doped. For poly(4‐vinylpyridine), we were unable to obtain stable dispersions of in chloroform–water dispersions.…”

Section: Resultsmentioning

confidence: 99%

“…A common expectation is that the interfaces between the nanoparticles may act as barriers for charge transport . We and others have shown that the interfaces between polymer nanoparticles do not impede “electronic” charge transport . Electronic charge transport and ion transport have different molecular packing requirements .…”

Section: Introductionmentioning

confidence: 99%

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Mixed Ionic–Electronic Conduction in Binary Polymer Nanoparticle Assemblies

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Bag

et al. 2017

Adv Materials Inter

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transistors. [5] Polymer-based MIECs contain two principal components, one for electronic conduction and the other for ionic conduction. Each of these components should meet the molecular packing requirements for charge transport and both components should arrange in cocontinuous morphologies with percolation pathways for charge transport in three dimensions. Yet, achieving such structures relevant for MIECs has not been straightforward. At present, several different strategies are used to design and fabricate MIECs. They are: (1) mixing of conjugated polymers and polyelectrolytes [e.g., poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)], [5,6,8,9] (2) imbibing ionic fluids in conjugated polymer films, [11] (3) incorporating ion conducting side chains on conjugated polymers, [12][13][14][15][16] (4) ion-doped [17][18][19][20] or oxidized [21] conjugated polymers, and (5) diblock copoly mer with ion conducting and electronic conducting polymers as the constituent blocks [e.g., poly(3-hexylthiophene)-bpoly(ethylene oxide) (P3HT-b-PEO)]. [2,3] However, these methods do not afford separate and systematic control over the morphology and properties of the ionic and electronic conducting phases while keeping the overall morphology constant. The central problem is the lack of a general approach to control the molecular packing and morphology in MIECs. We report here an approach, based on polymer nanoparticle selfassembly, to fabricate polymer-based MIECs. This approach provides a pathway to achieve tailored molecular order for each component on the nanoscale (<100 nm) and targeted assembly of the components on the mesoscale (>100 nm-100 µm). We demonstrate the efficacy of this approach for fabricating MIECs through binary nanoparticle assemblies of electronically conducting and Li-ion conducting polymer nanoparticles (see Figure 1a).Nanoparticle self-assembly is emerging as a powerful tool to design and fabricate mesoscale assemblies and interfaces. [22][23][24][25] For polymer-based materials, they provide a unique pathway to generate complex structures and co-assemblies under nonequilibrium processing conditions with macroscopic homogeneity and compositional flexibility. In this strategy, we first fabricate polymer components as nanoparticles, and then use them as building blocks for further assembly to create Polymer-based mixed ionic-electronic conductors (MIECs) are desired for both bulk and interfacial materials in next-generation energy storage and electronic devices. Polymer-based MIECs contain two principal components, one for electronic conduction and the other for ionic conduction. The central problem is the lack of a general approach to control the molecular packing and morphology of the constituent components that will afford the ability to easily tune transport properties. This study demonstrates the efficacy of a modular method based on polymer nanoparticle self-assembly to achieve MIECs with tunable conductivity. This work uses poly(3-hexylthiophene) nanoparticles as the electronic conductor and li...

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Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

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Mixed Ionic–Electronic Conduction in Binary Polymer Nanoparticle Assemblies

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Bag

et al. 2017

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“…The function

p_{i} (r)

as obtained from mixed QE2 model transforms smoothly from allow to disallow charge transfer scenarios of QE2 model as the values of r increase, but such smooth transition is not prominent for the dimer system, since the amount of charge transfer between two water molecules is very small. We expect that such transition may be visible for efficient charge conducting materials . Additionally, we mapped the bond charges of the system to atomic and molecular charges and the results are presented in the Supporting Information (see Figs.…”

Section: Resultsmentioning

confidence: 99%

“…However, it is physically more realistic to assign charges based on the electron density, which depend on their environment in a molecular system. Results of studies based on

a b i n i t i o

and density functional theory from the past decade have begun to point to the significance of charge transfer effects related to a broad class of physical, chemical, and biological systems . Roux, Klein, and their coworkers have demonstrated the nontrivial effects of charge transfer in the selectivity filter of the KcsA potassium‐selective ion channel .…”

Section: Introductionmentioning

confidence: 99%

A charge equilibration formalism for treating charge transfer effects in MD simulations: Application to water clusters

2017

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Conventional classical force fields by construction do not explicitly partition intermolecular interactions to include polarization and charge transfer effects, whereas fully quantum mechanical treatments allow a means to effect this dissection (although not uniquely due to the lack of a charge transfer operator). Considering the importance of polarization in a variety of systems, a particular class of classical models, charge equilibration models, have been extensively developed to study those systems; since these types of interaction models are inherently based on movement of charge throughout a system, they are natural platform for including polarization and charge transfer effects within the context of molecular simulations. Here, we present two bond-space charge equilibration models we term as QE2 and mixed QE2 treat charge transfer in classical molecular mechanical calculations those provide practical solutions to two major drawbacks of charge equilibration models: (a) a nonvanishing amount of charge transfer between two heteroatoms at large separations, and (b) superlinear polarizability scaling during bond dissociation due to charge transfer over unphysical, large distances. To control charge transfer during dissociation of a bond in a molecular system, we introduce a distance-dependent scaling function (QE2 model) which, controls and recovers physical behavior of the homonuclear and heteronuclear charge transfer between two atoms at small and large values of internuclear separation; and the mixed QE2 model in which we combine the QE2 model under allow and disallow charge transfer situations that describe both charge transfer and polarizability in a distance-dependent manner. We demonstrate the utility of both models in the case of a water dimer, and compare the results with other existing models, and further, we perform short molecular dynamics simulations for few water clusters with the QE2 model to show the charge transfer and internuclear separation are correlated in dynamics. © 2017 Wiley Periodicals, Inc.

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Organic Semiconductors Processed from Synthesis‐to‐Device in Water

et al. 2020

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Organic semiconductors (OSCs) promise to deliver next‐generation electronic and energy devices that are flexible, scalable and printable. Unfortunately, realizing this opportunity is hampered by increasing concerns about the use of volatile organic compounds (VOCs), particularly toxic halogenated solvents that are detrimental to the environment and human health. Here, a cradle‐to‐grave process is reported to achieve high performance p‐ and n‐type OSC devices based on indacenodithiophene and diketopyrrolopyrrole semiconducting polymers that utilizes aqueous‐processes, fewer steps, lower reaction temperatures, a significant reduction in VOCs (>99%) and avoids all halogenated solvents. The process involves an aqueous mini‐emulsion polymerization that generates a surfactant‐stabilized aqueous dispersion of OSC nanoparticles at sufficient concentration to permit direct aqueous processing into thin films for use in organic field‐effect transistors. Promisingly, the performance of these devices is comparable to those prepared using conventional synthesis and processing procedures optimized for large amounts of VOCs and halogenated solvents. Ultimately, the holistic approach reported addresses the environmental issues and enables a viable guideline for the delivery of future OSC devices using only aqueous media for synthesis, purification and thin‐film processing.

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Efficient Charge Transport in Assemblies of Surfactant‐Stabilized Semiconducting Nanoparticles

Cited by 43 publications

References 27 publications

Mixed Ionic–Electronic Conduction in Binary Polymer Nanoparticle Assemblies

Mixed Ionic–Electronic Conduction in Binary Polymer Nanoparticle Assemblies

A charge equilibration formalism for treating charge transfer effects in MD simulations: Application to water clusters

Organic Semiconductors Processed from Synthesis‐to‐Device in Water

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