High Thermoelectric Performance in Solution-Processed Semicrystalline PEDOT:PSS Films by Strong Acid-Base Treatment: Limitations and Potential.

Thermoelectric (TE) generation with solution-processable conducting polymers offers substantial potential in low-temperature energy harvesting based on high tunability in materials, processes, and form-factors. However, manipulating the TE and charge transport properties accompanies structural and energetic disorders, restricting the enhancement of thermoelectric power factor (PF). Here, solution-based strong acid-base treatment techniques are introduced to modulate the doping level of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films with preserving its molecular orientation, enabling to achieve a remarkably high PF of 534.5 µW m-1  K-2 . Interestingly, theoretical modeling suggested that further de-doping can increase the PF beyond the experimental value. However, it is impossible to reach this value experimentally, even without any degradation of PEDOT crystallinity. Uncovering the underlying reason for the limitation, an analysis of the relationship among the microstructure-thermoelectric performance-charge transport property revealed that inter-domain connectivity via tie-chains and the resultant percolation for transport are crucial factors in achieving high TE performance, as in charge transport. It is believed that the methods and fundamental understandings in this work would contribute to the exploitation of conducting polymer-based low-temperature energy harvesting.

Molecular Engineering for Enhanced Thermoelectric Performance of Single-Walled Carbon Nanotubes/π-Conjugated Organic Small Molecule Hybrids.

Hybridizing single-walled carbon nanotubes (SWCNTs) with π-conjugated organic small molecules (π-OSMs) offers a promising approach for producing high-performance thermoelectric (TE) materials through the facile optimization of the molecular geometry and energy levels of π-OSMs. Designing a twisted molecular structure for the π-OSM with the highest occupied molecular orbital energy level comparable to the valence band of SWCNTs enables effective energy filtering between the two materials. The SWCNTs/twisted π-OSM hybrid exhibits a high Seebeck coefficient of 110.4 ± 2.6 µV K-1 , leading to a significantly improved power factor of 2,136 µW m-1 K-2 , which is 2.6 times higher than that of SWCNTs. Moreover, a maximum figure of merit over 0.13 at room temperature is achieved via the efficient TE transport of the SWCNTs/twisted π-OSM hybrid. The study highlights the promising potential of optimizing molecular engineering of π-OSMs for hybridization with SWCNTs to create next-generation, efficient TE materials.

Ambient-Stable n-Type Carbon Nanotube/Organic Small-Molecule Thermoelectrics Enabled by Energy Level Control.

The stability of n-type organic and hybrid thermoelectric materials is limited in terms of their practical application to p-n parallel thermoelectric devices. We demonstrate the ambient stability of an n-type single-walled carbon nanotube/organic small-molecule (SWNT/OSM) hybrid by deepening the lowest occupied molecular orbital energy level. This hybrid exhibited the best figure of merit (0.032) among n-type SWNT/OSM hybrid thermoelectrics and an enhanced power factor of 291.0 µW m-1 K-2. Furthermore, we observed that the n-type thermoelectric stability of a hybrid of SWNT and pip containing two N-ethylpiperidinyl groups on both sides of a naphthalenediimide core was retained at 87% over 7 months (220 days) under ambient conditions without encapsulation.

Supramolecular Functionalization for Improving Thermoelectric Properties of Single-Walled Carbon Nanotubes-Small Organic Molecule Hybrids.

Single-walled carbon nanotube (SWCNTs-P)-small organic molecule hybrid materials are promising candidates for achieving high thermoelectric (TE) performance. In this study, we synthesized rod-coil amphiphilic molecules, that is, tri(ethylene oxide) chain-attached bis(bithiophenyl)-terphenyl derivatives (1 and 2). Supramolecular functionalization of SWCNTs-P with 1 or 2 induced charge-transfer interactions between them. Improved TE properties of the supramolecular hybrids (SWCNTs-1 and SWCNTs-2) are attributed to increased charge-carrier concentration (electrical conductivity), interfacial phonon scattering (thermal conductivity), and energy difference between the transport and Fermi levels (ETr - EF; Seebeck coefficient). SWCNTs-2 exhibited a ZT of 0.42 × 10-2 at 300 K, which is 350% larger than that of SWCNTs-P. Furthermore, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ)-doped SWCNTs-2 showed the highest ZT value of 1.96 × 10-2 at 300 K among SWCNTs-P/small organic molecule hybrids known until now. These results demonstrated that the supramolecular functionalization of SWCNTs-P with small organic molecules could be useful for enhancement of TE performance and applications in wearable/flexible thermoelectrics.

Enhanced Humid Reliability of Organic Thermoelectrics via Crosslinking with Glycerol.

Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has shown significant achievements in organic thermoelectrics (TEs) as an alternative for inorganic counterparts. However, PEDOT:PSS films have limited practical applications because their performance is sensitive to humidity. Crosslinking additives are utilized to improve the reliability of PEDOT:PSS film through enhancing hydrophobicity; among these, polyethylene glycol (PEG) is a widely-used additive. However, ether groups in PEG induce water molecules in the film through the hydrogen bond, which deteriorates the TE reliability. Here, we enhance the TE reliability of the PEDOT:PSS film using glycerol as an additive through the crosslinking reaction between the hydroxyl group in glycerol and the sulfonic acid in PEDOT:PSS. The TE reliability (1/Power factor (PF)) of PEG solution-treated PEDOT:PSS film (PEG solution-treated film) was 57% of its initial absolute value (0 h), after 288 h (two weeks) in a humid environment (95% relative humidity, 27 °C temperature). On the other hand, the glycerol solution-treated PEDOT:PSS film (glycerol solution-treated film) exhibited superior TE reliability and preserved 75% of its initial 1/PF. Furthermore, glycerol vapor treatment enabled the film to have stronger TE humid reliability, maintaining 82% of its initial 1/PF, with the same condition. This enhancement is attributed to the increased hydrophobicity and lower oxygen content of the glycerol vapor-treated PEDOT:PSS film (glycerol vapor-treated film), which provides little change in the chemical composition of PEDOT:PSS.

Structural and Morphological Evolution for Water-resistant Organic Thermoelectrics.

We systematically investigated the effect of 2,5-bis(2-hydroxy-3-methacryloyloxypropoxy)-1,4:3,6-dianhydro-sorbitol (Iso-GMA) with different concentrations on the structural and morphological evolution of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) containing a fixed volume of dimethyl sulfoxide (DMSO) to realize water-resistant organic thermoelectric devices. As an additive, Iso-GMA is a hydrophilic and crosslinking agent that can interact with PEDOT and PSS chains by hydrogen bonding and/or dipole-dipole- or dipole-charge-interaction. The Seebeck coefficient and power factor in the film incorporating 3.0 vol% DMSO and 0.8 vol% Iso-GMA were respectively 1.82 × 102 and 1.53 × 105% higher than those of the pristine PEDOT:PSS film without additives (DMSO and Iso-GMA). These results can be attributed to the self-assembled and crosslinked fibril networks with optimized phase separation, where the film has densely-packed PEDOT and highly lamellar-stacked PSS. Also, the reduced charge carrier concentration from the structural characteristics originated in the higher thermoelectric properties. We introduced the schematic illustration to understand the chemical bonding among the components and the morphological evolution according to the Iso-GMA concentration. The increased mechanical strength by the interchain stacking degree of PEDOT and the crosslinking of Iso-GMA facilitate the film remained in a water bath for 0.5 h without physical degradation, and sustain the thermoelectric properties during 12 h in humid conditons.

Correlations of Optical Absorption, Charge Trapping, and Surface Roughness of TiO2 Photoanode Layer Loaded with Neat Ag-NPs for Efficient Perovskite Solar Cells.

We systematically investigated the effect of silver nanoparticles (Ag-NPs) on the power conversion efficiency (PCE) of perovskite solar cells (PSCs). Neat, spherical Ag-NPs at loading levels of 0.0, 0.5, 1.0, and 2.0 wt % were embedded into the titanium dioxide (TiO2) photoanode layer. The plasmonic effect of the Ag-NPs strongly enhanced the incident light absorption over a wide range of the visible wavelength region in addition to the inherent absorbance of the perovskite sensitizer. The low conduction energy level of the Ag-NPs compared to that of TiO2 provides trap sites for free charge carriers. Thus, the correlation between the enhancement of the optical absorption and the number of charge traps provided by the Ag-NPs is critical to determine the device performance, especially current density (Jsc) and PCE. This is confirmed by the quantitative comparison of the incident light absorption and the time-resolved photoluminescence decay according to the loading levels of the Ag-NPs in the TiO2 layer. The absorption enhancement from 380 to 750 nm in the UV-visible spectrum is proportional to the increase in the loading levels of the Ag-NPs. However, the Jsc increases with the device with 0.5 wt % Ag-NPs and gradually decreases with increases in the loading level above 0.5 wt % because of the different contributions to the absorbance and the charge trapping by different Ag-NP loading levels. In addition, the suppression of the surface roughness with dense packing by the Ag-NPs helps to improve the Jsc and the following PCE. Consequently, the PCE of the PSC with 0.5 wt % Ag-NPs is increased to 11.96%. These results are attributed to the balance between increased absorbance by the localized surface plasmon resonance and the decreased charge trapping as well as the decreased surface roughness of the TiO2 layer with the Ag-NPs.

Antibody functionalization with a dual reactive hydrazide/click crosslinker.

A water-soluble, dual reactive hydrazide/click crosslinker (ethynyl hydrazide, EH) was synthesized and characterized. A model antibody, human immunoglobulin G (hIgG), was ethynylated by conventional oxidation/hydrazide reactions with the hydrazide moiety of EH. The terminal alkyne conjugated to the glycan of hIgG was easily functionalized by quantitative and bioorthogonal Cu(I)-catalyzed azide-alkyne cycloaddition. The potential of the hydrazide/click crosslinker as a reagent to functionalize antibodies was demonstrated with fluorophore labeling and antibody immobilization.