Closing the Stability-Performance Gap in Organic Thermoelectrics by Adjusting the Partial to Integer Charge Transfer Ratio.

Two doping mechanisms are known for the well-studied materials poly(3-hexylthiophene) (P3HT) and poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), namely, integer charge transfer (ICT) and charge transfer complex (CTC) formation. Yet, there is poor understanding of the effect of doping mechanism on thermal stability and the thermoelectric properties. In this work, we present a method to finely adjust the ICT to CTC ratio. Using it, we characterize electrical and thermal conductivities as well as the Seebeck coefficient and the long-term stability under thermal stress of P3HT and PBTTT of different ICT/CTC ratios. We establish that doping through the CTC results in more stable, yet lower conductivity samples compared to ICT doped films. Importantly, moderate CTC fractions of ∼33% are found to improve the long-term stability without a significant sacrifice in electrical conductivity. Through visible and IR spectroscopies, polarized optical microscopy, and grazing-incidence wide-angle X-ray scattering, we find that the CTC dopant molecule access sites within the polymer network are less prone to dedoping upon thermal exposure.

Farming thermoelectric paper.

Waste heat to electricity conversion using thermoelectric generators is emerging as a key technology in the forthcoming energy scenario. Carbon-based composites could unleash the as yet untapped potential of thermoelectricity by combining the low cost, easy processability, and low thermal conductivity of biopolymers with the mechanical strength and good electrical properties of carbon nanotubes (CNTs). Here we use bacteria in environmentally friendly aqueous media to grow large area bacterial nanocellulose (BC) films with an embedded highly dispersed CNT network. The thick films (≈10 µm) exhibit tuneable transparency and colour, as well as low thermal and high electrical conductivity. Moreover, they are fully bendable, can conformally wrap around heat sources and are stable above 500 K, which expands the range of potential uses compared to typical conducting polymers and composites. The high porosity of the material facilitates effective n-type doping, enabling the fabrication of a thermoelectric module from farmed thermoelectric paper. Because of vertical phase separation of the CNTs in the BC composite, the grown films at the same time serve as both the active layer and separating layer, insulating each thermoelectric leg from the adjacent ones. Last but not least, the BC can be enzymatically decomposed, completely reclaiming the embedded CNTs.

Tuning thermal transport in ultrathin silicon membranes by surface nanoscale engineering.

A detailed understanding of the connections of fabrication and processing to structural and thermal properties of low-dimensional nanostructures is essential to design materials and devices for phononics, nanoscale thermal management, and thermoelectric applications. Silicon provides an ideal platform to study the relations between structure and heat transport since its thermal conductivity can be tuned over 2 orders of magnitude by nanostructuring. Combining realistic atomistic modeling and experiments, we unravel the origin of the thermal conductivity reduction in ultrathin suspended silicon membranes, down to a thickness of 4 nm. Heat transport is mostly controlled by surface scattering: rough layers of native oxide at surfaces limit the mean free path of thermal phonons below 100 nm. Removing the oxide layers by chemical processing allows us to tune the thermal conductivity over 1 order of magnitude. Our results guide materials design for future phononic applications, setting the length scale at which nanostructuring affects thermal phonons most effectively.