An official website of the United States government
A novel n-type copolymer dopant polystyrene-polyvinyl hexylpyridinium fluoride (PSpF) with fluoride anion is designed and synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. To our knowledge, it is the first polymeric fluoride dopant. Electrical conductivity of 4.2 S cm-1 and high power factor of 67 μW m-1 K-2 are achieved for PSpF doped polymer films, with a corresponding decrease in thermal conductivity as the PSpF concentration is increased, giving the highest ZT of 0.1. An especially high electrical conductivity of 58 S cm-1 at 88 ℃ and outstanding thermal stability were recorded. Further, organic transistors of PSpF-doped thin films exhibit high electron mobility and Hall mobility of 0.86 and 1.70 cm2 V-1 s-1, respectively. The results suggest that polystyrene-polyvinyl pyridinium salt copolymers with fluoride anion are promising for high performance n-type all-polymer thermoelectrics. This work provides a new way to realize organic thermoelectrics with high conductivity relative to Seebeck coefficient, high power factor, thermal stability and broad processing window.
more »
« less
3,4,5‐Trimethoxy Substitution on an N‐DMBI Dopant with New N‐type Polymers: Polymer‐Dopant Matching for Improved Conductivity‐Seebeck Coefficient Relationship
Achieving high electrical conductivity and thermoelectric power factor simultaneously for n-type organic thermoelectrics is still challenging. By constructing two new acceptor-acceptor n-type conjugated polymers with different backbones and introducing the 3,4,5-trimethoxyphenyl group to form the new n-type dopant 1,3-dimethyl-2-(3,4,5-trimethoxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole (TP-DMBI), high electrical conductivity of 11 S cm-1 and power factor of 32 μW m-1 K-2 are achieved. Calculations using Density Functional Theory show that TP-DMBI presents a higher singly occupied molecular orbital (SOMO) energy level of -1.94 eV than that of the common dopant 4-(1, 3-dimethyl-2, 3-dihydro-1H-benzoimidazol-2-yl) phenyl) dimethylamine (N-DMBI) (-2.36 eV), which can result in a larger offset between the SOMO of dopant and lowest unoccupied molecular orbital (LUMO) of n-type polymers, though that effect may not be dominant in the present work. The doped polymer films exhibit higher Seebeck coefficient and power factor than films using N-DMBI at the same doping levels or similar electrical conductivity levels. Moreover, TP-DMBI doped polymer films offer much higher electron mobility of up to 0.53 cm2 V-1 s-1 than films with N-DMBI doping, demonstrating the potential of TP-DMBI, and 3,4,5-trialkoxy DMBIs more broadly, for high performance n-type organic thermoelectrics.
more »
« less
- PAR ID:
- 10301301
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)N-type semiconducting polymers have been recently utilized in thermoelectric devices, however they have typically exhibited low electrical conductivities and poor device stability, in contrast to p-type semiconductors, which have been much higher performing. This is due in particular to the n-type semiconductor's low doping efficiency, and poor charge carrier mobility. Strategies to enhance the thermoelectric performance of n-type materials include optimizing the electron affinity (EA) with respect to the dopant to improve the doping process and increasing the charge carrier mobility through enhanced molecular packing. Here, we report the design, synthesis and characterization of fused electron-deficient n-type copolymers incorporating the electron withdrawing lactone unit along the backbone. The polymers were synthesized using metal-free aldol condensation conditions to explore the effect of enlarging the central phenyl ring to a naphthalene ring, on the electrical conductivity. When n-doped with N-DMBI, electrical conductivities of up to 0.28 S cm −1 , Seebeck coefficients of −75 μV K −1 and maximum Power factors of 0.16 μW m −1 K −2 were observed from the polymer with the largest electron affinity of −4.68 eV. Extending the aromatic ring reduced the electron affinity, due to reducing the density of electron withdrawing groups and subsequently the electrical conductivity reduced by almost two orders of magnitude.more » « less
-
Abstract A new approach to control the n‐doping reaction of organic semiconductors is reported using surface‐functionalized gold nanoparticles (f‐AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n‐type dopant precursor N‐DMBI‐H with several molecular and polymeric semiconductors at different temperatures with/without f‐AuNPs, vis‐à‐vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f‐AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10–140 S cm−1). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n‐doped films in opto‐electronic devices such as thin‐film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.more » « less
-
Molecular doping can increase the conductivity of organic semiconductors and plays an increasingly important role in emerging and established plastic electronics applications. 4-(1,3-Dimethyl-2,3-dihydro-1 H -benzimidazol-2-yl)- N , N -dimethylaniline (N-DMBI-H) and tris(pentafluorophenyl)borane (BCF) are established n- and p-dopants, respectively, but neither functions as a simple one-electron redox agent. Molecular hydrogen has been suggested to be a byproduct in several proposed mechanisms for doping using both N-DMBI-H and BCF. In this paper we show for the first time the direct detection of molecular hydrogen in the uncatalysed doping of a variety of polymeric and molecular semiconductors using these dopants. Our results provide insight into the doping mechanism, providing information complementary to that obtained from more commonly applied methods such as optical, electron spin resonance, and electrical measurements.more » « less
-
This paper investigates the microscale engineering aspects of n-type doped GaSb to address the challenges associated with achieving high electrical conductivity and precise dopant distribution in this semiconductor material. AC impedance spectroscopy is employed as a reliable technique to characterize the microstructural and electrical properties of GaSb, providing valuable insights into the impact of grain boundaries on overall electrical performance. The uneven distribution of dopants, caused by diffusion, and the incomplete activation of introduced dopants pose significant obstacles in achieving consistent material properties. To overcome these challenges, a careful selection of alloying elements, such as bismuth, is explored to suppress the formation of native acceptor defects and modulate band structures, thereby influencing the doping and compensator formation processes. Additionally, the paper examines the effect of microwave annealing as a potential solution for enhancing dopant activation, minimizing diffusion, and reducing precipitate formation. Microwave annealing shows promise due to its rapid heating and shorter processing times, making it a viable alternative to traditional annealing methods. The study underscores the need for a stable grain boundary passivation strategy to achieve significant improvements in GaSb material performance. Simple grain size reduction strategies alone do not result in better thermoelectric performance, for example, and increasing the grain boundary area per unit volume exacerbates the issue of free carrier compensation. These findings highlight the complexity of achieving optimal doping in GaSb materials and the importance of innovative analytical techniques and controlled doping processes. The comprehensive exploration of n-type doped GaSb presented in this research provides valuable insights for future advancements in the synthesis and optimization of high-conductivity nanostructured n-type GaSb, with potential applications in thermoelectric devices and other electronic systems.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/anie.202110505
