Stable and reproducible current-controlled bistable electrical switching has been observed in polycrystalline organic semiconducting films. The effect has been observed in a lamellar structure with a film of microcrystalline Cu-TCNQ between Cu and Al electrodes where the Cu-TCNQ is grown on a Cu substrate via a spontaneous electrolysis technique. The switching effect is insensitive to moisture and is observed over a large temperature range. The current-voltage characteristics reveal an abrupt decrease in impedance from 2 MΩ to less than 200 Ω at a field strength of 4×103 V/cm. The transition from a high- to low-impedance state occurs with delay and switching times of approximately 15 and 10 nsec, respectively. Switching with high-power dissipation yields a low-impedance memory state which can be erased by application of a short current pulse. An interpretation of this behavior is based on the bulk properties of the mixed valence semiconductor Cu-TCNQ.
This perspective discusses theories of polymer thermoelectrics, identifying combinations of electronic charge carrier energies and thermal conductivity mechanisms that could lead to the highest efficiencies. Structures, electrical conductivities, Seebeck coefficients, and figures of merit are summarized for some recently devised polymer-based thermoelectric materials. Foundational equations that define these quantities are presented, and are related to thermal conductivities as well. Finally, approaches to polymer composite design that optimize thermoelectric performance in light of the theoretical models are proposed.
Polymer thermoelectrics state of the artPolymer thermoelectrics have been reviewed very recently. 1 A second paper includes concise review charts of thermoelectric parameters of polymers. 2 Rather than reiterating all the details found in those prior publications, we include a brief background summary here, interleaving selected examples from the very latest work.Among the polymers for which Seebeck coefficients (S) and accompanying electrical conductivities s have been measured are
Semiconducting organometallic films such as copper tetracyanoquinodimethane (CuTCNQ) have been observed to switch between two stable states when exposed to optical radiation. Observations of switching between two states in these films have been made by Raman spectroscopic methods and direct observation of electrical resistance changes. Line or pattern generation is observed for exposure above certain threshold levels. These effects are observed in a wide range of Cu and Ag organometallic compounds.
Strong interest in energy generation and storage has yielded excellent progress on organic based solar cells, and there is also a strong desire for equivalent advancement in polymer-based charge storage devices such as batteries and super-capacitors. Despite extensive research on electronically conducting polymers including polypyrrole, polythiophene, and polyaniline, limitations to the maximum doping density and chemical stability had been considered a significant restriction on the development of polymer batteries. Recent work appears to show a meaningful increase in the upper bound of the maximum density from 0.5 to 1.0 electrons per monomer depending on the structure, processing, and ionic species used in charging and discharging of the polymers. Several recent examples have also implied that more stable, reversible charge-discharge cycling is being observed in n-doped polymers. These observations suggest that the performance metrics of this class of electronically conducting polymer may ultimately reach the levels required for practical battery applications. Further efforts are essential to perfect practical large-scale electrode fabrication to move toward greater compatibility in the methods used for solar cells and those used in producing batteries. A better understanding must also be developed to elucidate the effects of molecular structure and polymer architecture on these materials.
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