Three-Dimensional Graphene Sheet-Carbon Veil Thermoelectric Composite with Microinterfaces for Energy Applications.

Over the years, various processing techniques have been explored to synthesize three-dimensional graphene (3DG) composites with tunable properties for advanced applications. In this work, we have demonstrated a new procedure to join a 3D graphene sheet (3DGS) synthesized by chemical vapor deposition (CVD) with a commercially available carbon veil (CV) via cold rolling to create 3DGS-CV composites. Characterization techniques such as scanning electron microscopy (SEM), Raman mapping, X-ray diffraction (XRD), electrical resistance, tensile strength, and Seebeck coefficient measurements were performed to understand various properties of the 3DGS-CV composite. Extrusion of 3DGS into the pores of CV with multiple microinterfaces between 3DGS and the graphitic fibers of CV was observed, which was facilitated by cold rolling. The extruded 3D graphene revealed pristine-like behavior with no change in the shape of the Raman 2D peak and Seebeck coefficient. Thermoelectric (TE) power generation and photothermoelectric responses have been demonstrated with in-plane TE devices of various designs made of p-type 3DGS and n-type CV couples yielding a Seebeck coefficient of 32.5 µV K-1. Unlike various TE materials, 3DGS, CV, and the 3DGS-CV composite were very stable at high relative humidity. The 3DGS-CV composite revealed a thin, flexible profile, good moisture and thermal stability, and scalability for fabrication. These qualities allowed it to be successfully tested for temperature monitoring of a Li-ion battery during charging cycles and for large-area temperature mapping.

Performance Optimization and Exergy Analysis of Thermoelectric Heat Recovery System for Gas Turbine Power Plants.

Thermoelectric (TE) waste heat recovery has attracted significant attention over the past decades, owing to its direct heat-to-electricity conversion capability and reliable operation. However, methods for application-specific, system-level TE design have not been thoroughly investigated. This work provides detailed design optimization strategies and exergy analysis for TE waste heat recovery systems. To this end, we propose the use of TE system equipped on the exhaust of a gas turbine power plant for exhaust waste heat recovery and use it as a case study. A numerical tool has been developed to solve the coupled charge and heat current equations with temperature-dependent material properties and convective heat transfer at the interfaces with the exhaust gases at the hot side and with the ambient air at the heat sink side. Our calculations show that at the optimum design with 50% fill factor and 6 mm leg thickness made of state-of-the-art Bi2Te3 alloys, the proposed system can reach power output of 10.5 kW for the TE system attached on a 2 m-long, 0.5 × 0.5 m2-area exhaust duct with system efficiency of 5% and material cost per power of 0.23 $/W. Our extensive exergy analysis reveals that only 1% of the exergy content of the exhaust gas is exploited in this heat recovery process and the exergy efficiency of the TE system can reach 8% with improvement potential of 85%.

Boosting Thermoelectric Power Factor of Carbon Nanotube Networks with Excluded Volume by Co-Embedded Microparticles.

Carbon nanotube (CNT) networks embedded in a polymer matrix have been extensively studied as a flexible thermoelectric transport medium over the recent years. However, their power factor has been largely limited by the relatively inefficient tunneling transport at junctions between CNTs and the low-density conducting channels throughout the networks. This work demonstrates that significant power factor enhancements can be achieved by adding electrically insulating microscale particles in three-dimensional CNT networks embedded in the polymer matrix. When silica particles of a few µm diameters were co-embedded in single-walled CNT (SWCNT)-polydimethylsiloxane (PDMS) composites, both the electrical conductivity and the Seebeck coefficient were simultaneously enhanced, thereby boosting the power factor by more than a factor of six. We found that the silica microparticles excluded a large volume of the composite from the access of CNTs and caused CNT networks to form around them with the polymer as a binder, resulting in improved network connectivity and alignment of CNTs. Our theoretical calculations based on junction tunneling transport for three-dimensional CNT networks show that the significant power factor enhancement can be attributed to the enhanced tunneling with reduced junction distance between CNTs. Additional power factor enhancement by a factor of three was achieved by sample compression, which further reduced the mean junction distance to enhance tunneling but also reduced the geometric factor at the same time, limiting the enhancement of electrical conductivity.

Far-field thermal imaging below diffraction limit.

Non-uniform self-heating and temperature hotspots are major concerns compromising the performance and reliability of submicron electronic and optoelectronic devices. At deep submicron scales where effects such as contact-related artifacts and diffraction limits accurate measurements of temperature hotspots, non-contact thermal characterization can be extremely valuable. In this work, we use a Bayesian optimization framework with generalized Gaussian Markov random field (GGMRF) prior model to obtain accurate full-field temperature distribution of self-heated metal interconnects from their thermoreflectance thermal images (TRI) with spatial resolution 2.5 times below Rayleigh limit for 530nm illumination. Finite element simulations along with TRI experimental data were used to characterize the point spread function of the optical imaging system. In addition, unlike iterative reconstruction algorithms that use ad hoc regularization parameters in their prior models to obtain the best quality image, we used numerical experiments and finite element modeling to estimate the regularization parameter for solving a real experimental inverse problem.

Recent advances in printable thermoelectric devices: materials, printing techniques, and applications.

Thermoelectric devices have great potential as a sustainable energy conversion technology to harvest waste heat and perform spot cooling with high reliability. However, most of the thermoelectric devices use toxic and expensive materials, which limits their application. These materials also require high-temperature fabrication processes, limiting their compatibility with flexible, bio-compatible substrate. Printing electronics is an exciting new technique for fabrication that has enabled a wide array of biocompatible and conformable systems. Being able to print thermoelectric devices allows them to be custom made with much lower cost for their specific application. Significant effort has been directed toward utilizing polymers and other bio-friendly materials for low-cost, lightweight, and flexible thermoelectric devices. Fortunately, many of these materials can be printed using low-temperature printing processes, enabling their fabrication on biocompatible substrates. This review aims to report the recent progress in developing high performance thermoelectric inks for various printing techniques. In addition to the usual thermoelectric performance measures, we also consider the attributes of flexibility and the processing temperatures. Finally, recent advancement of printed device structures is discussed which aims to maximize the temperature difference across the junctions.

Gigantic Phonon-Scattering Cross Section To Enhance Thermoelectric Performance in Bulk Crystals.

In thermoelectric energy conversions, thermal conductivity reduction is essential for enhancing thermoelectric performance while maintaining a high power factor. Herein, we propose an approach based on coated-grain structures to effectively reduce the thermal conductivity to a much greater degree when compared to that done by conventional nanodot nanocomposite. By incorporating CdTe coated layers on the surface of SnTe grains, the thermal conductivity is as low as 1.16 W/m-K at 929 K, resulting in a thermoelectric figure of merit, i.e., zT, of 1.90. According to our developed theory, phonons scatter coherently due to the phase lag between phonons passing through and around the coated grain. Such scattering is induced by the acoustic impedance mismatch between the coated layer and the grain, resulting in a gigantic phonon-scattering cross section. The phonon-scattering cross section of the coated grains is several orders of magnitude larger than that of the nanodots with the same impurity concentration. The power factor was also slightly increased by the energy filtering effect at the coated surface and additional minority carrier blocking by the heterointerfaces. This scheme can be utilized for various bulk crystals, meaning a broad range of materials can be considered for thermoelectric applications.

Ion Write Microthermotics: Programing Thermal Metamaterials at the Microscale.

Considerable advances in manipulating heat flow in solids have been made through the innovation of artificial thermal structures such as thermal diodes, camouflages, and cloaks. Such thermal devices can be readily constructed only at the macroscale by mechanically assembling different materials with distinct values of thermal conductivity. Here, we extend these concepts to the microscale by demonstrating a monolithic material structure on which nearly arbitrary microscale thermal metamaterial patterns can be written and programmed. It is based on a single, suspended silicon membrane whose thermal conductivity is locally, continuously, and reversibly engineered over a wide range (between 2 and 65 W/m·K) and with fine spatial resolution (10-100 nm) by focused ion irradiation. Our thermal cloak demonstration shows how ion-write microthermotics can be used as a lithography-free platform to create thermal metamaterials that control heat flow at the microscale.

High thermoelectric power-factor composites based on flexible three-dimensional graphene and polyaniline.

Hybrid thermoelectric (TE) nanocomposites containing conducting polymers and nanocarbon materials have been extensively studied in recent years due to their unique advantages over single-phase organic/inorganic TE materials. Nanocarbon materials have been developed as conductive nanofillers to improve the electrical conductivity of the polymer matrix, and to create a strong π-π interfacial interaction with the matrix to enhance the TE performance. However, previous designs of the hybrid TE nanocomposites tend to cause aggregation of nanocarbon materials, which is detrimental to the TE performance. Also, they are limited in their fabrication to thin film technologies with submicron thicknesses, which prevents these composites from being used in practical TE devices. Herein, we present the synthesis and thermoelectric properties of free-standing, three-dimensional graphene (3DG)-polyaniline (PANI) composites with greater than 100 µm thicknesses for high performance flexible p-type thermoelectrics. Our 3DG matrix has been synthesized by Chemical Vapor Deposition (CVD) with particulate nickel catalysts, and used as a scaffold for the polymer composites. This material provides an excellent electrical conductivity and a reasonable Seebeck coefficient along with very good mechanical integrity preserved when bending, thus making it a promising candidate for flexible TE. PANI polymer was electrochemically grown on the 3DG scaffold as a filler to further tune the TE properties. The proposed 3DG-PANI composites showed a maximum power factor of 81.9 µW m-1 K-2 with a PANI loading of 80 wt% and highly reproducible TE performance after repeated mechanical bending tests. This novel material provides a different strategy for simple and scalable fabrication of flexible thermoelectrics with high performance TE energy harvesting and improved mechanical properties.

Investigating enhanced thermoelectric performance of graphene-based nano-structures.

Recently, it has been demonstrated that graphene nano-ribbons (GNRs) exhibit superior thermoelectric performance compared to graphene sheets. However, the underlying mechanism behind this enhancement has not been systematically investigated and significant opportunity remains for further enhancement of the thermoelectric performance of GNRs by optimizing their charge carrier concentration. In this work, we modulate the carrier concentration of graphene-based nano-structures using a gate voltage and investigate the resulting carrier-concentration-dependent thermoelectric parameters using the Boltzmann transport equations. We investigate the effect of energy dependent scattering time and the role of substrate-induced charge carrier fluctuation in optimizing the Seebeck coefficient and power factor. Our approach predicts the scattering mechanism and the extent of the charge carrier fluctuation in different samples and explains the enhancement of thermoelectric performance of GNR samples. Subsequently, we propose a route towards the enhancement of thermoelectric performance of graphene-based devices which can also be applied to other two-dimensional materials.

Full-field thermal imaging of quasiballistic crosstalk reduction in nanoscale devices.

Understanding nanoscale thermal transport is of substantial importance for designing contemporary semiconductor technologies. Heat removal from small sources is well established to be severely impeded compared to diffusive predictions due to the ballistic nature of the dominant heat carriers. Experimental observations are commonly interpreted through a reduction of effective thermal conductivity, even though most measurements only probe a single aggregate thermal metric. Here, we employ thermoreflectance thermal imaging to directly visualise the 2D temperature field produced by localised heat sources on InGaAs with characteristic widths down to 100 nm. Besides displaying effective thermal performance reductions up to 50% at the active junctions in agreement with prior studies, our steady-state thermal images reveal that, remarkably, 1-3 µm adjacent to submicron devices the crosstalk is actually reduced by up to fourfold. Submicrosecond transient imaging additionally shows responses to be faster than conventionally predicted. A possible explanation based on hydrodynamic heat transport, and some open questions, are discussed.

Manipulating Band Structure through Reconstruction of Binary Metal Sulfide for High-Performance Thermoelectrics in Solution-Synthesized Nanostructured Bi13 S18 I2.

Reconstructing canonical binary compounds by inserting a third agent can significantly modify their electronic and phonon structures. Therefore, it has inspired the semiconductor communities in various fields. Introducing this paradigm will potentially revolutionize thermoelectrics as well. Using a solution synthesis, Bi2 S3 was rebuilt by adding disordered Bi and weakly bonded I. These new structural motifs and the altered crystal symmetry induce prominent changes in electrical and thermal transport, resulting in a great enhancement of the figure of merit. The as-obtained nanostructured Bi13 S18 I2 is the first non-toxic, cost-efficient, and solution-processable n-type material with z T=1.0.

Nanocomposites from Solution-Synthesized PbTe-BiSbTe Nanoheterostructure with Unity Figure of Merit at Low-Medium Temperatures (500-600 K).

A scalable, low-temperature solution process is used to synthesize precursor material for Pb-doped Bi0.7 Sb1.3 Te3 thermoelectric nanocomposites. The controllable Pb-doping leads to the increase in the optical bandgap, thus delaying the onset of bipolar conduction. Furthermore, the solution synthesis enables nanostructuring, which greatly reduces thermal conductivity. As a result, this material exhibits a zT = 1 over the 513-613 K range.

Thermal Transport Driven by Extraneous Nanoparticles and Phase Segregation in Nanostructured Mg2(Si,Sn) and Estimation of Optimum Thermoelectric Performance.

Solid solutions of magnesium silicide and magnesium stannide were recently reported to have high thermoelectric figure-of-merits (ZT) due to remarkably low thermal conductivity, which was conjectured to come from phonon scattering by segregated Mg2Si and Mg2Sn phases without detailed study. However, it is essential to identify the main cause for further improving ZT as well as estimating its upper bound. Here we synthesized Mg2(Si,Sn) with nanoparticles and segregated phases, and theoretically analyzed and estimated the thermal conductivity upon segregated fraction and extraneous nanoparticle addition by fitting experimentally obtained thermal conductivity, electrical conductivity, and thermopower. In opposition to the previous speculation that segregated phases intensify phonon scattering, we found that lattice thermal conductivity was increased by the phase segregation, which is difficult to avoid due to the miscibility gap. We selected extraneous TiO2 nanoparticles dissimilar to the host materials as additives to reduce lattice thermal conductivity. Our experimental results showed the maximum ZT was improved from ∼0.9 without the nanoparticles to ∼1.1 with 2 and 5 vol % TiO2 nanoparticles at 550 °C. According to our theoretical analysis, this ZT increase by the nanoparticle addition mainly comes from suppressed lattice thermal conductivity in addition to lower bipolar thermal conductivity at high temperatures. The upper bound of ZT was predicted to be ∼1.8 for the ideal case of no phase segregation and addition of 5 vol % TiO2 nanoparticles. We believe this study offers a new direction toward improved thermoelectric performance of Mg2(Si,Sn).

Enhanced thermoelectric properties in bulk nanowire heterostructure-based nanocomposites through minority carrier blocking.

To design superior thermoelectric materials the minority carrier blocking effect in which the unwanted bipolar transport is prevented by the interfacial energy barriers in the heterogeneous nanostructures has been theoretically proposed recently. The theory predicts an enhanced power factor and a reduced bipolar thermal conductivity for materials with a relatively low doping level, which could lead to an improvement in the thermoelectric figure of merit (ZT). Here we show the first experimental demonstration of the minority carrier blocking in lead telluride-silver telluride (PbTe-Ag2Te) nanowire heterostructure-based nanocomposites. The nanocomposites are made by sintering PbTe-Ag2Te nanowire heterostructures produced in a highly scalable solution-phase synthesis. Compared with Ag2Te nanowire-based nanocomposite produced in similar method, the PbTe-Ag2Te nanocomposite containing ∼5 atomic % PbTe exhibits enhanced Seebeck coefficient, reduced thermal conductivity, and ∼40% improved ZT, which can be well explained by the theoretical modeling based on the Boltzmann transport equations when energy barriers for both electrons and holes at the heterostructure interfaces are considered in the calculations. For this p-type PbTe-Ag2Te nanocomposite, the barriers for electrons, that is, minority carriers, are primarily responsible for the ZT enhancement. By extending this approach to other nanostructured systems, it represents a key step toward low-cost solution-processable nanomaterials without heavy doping level for high-performance thermoelectric energy harvesting.

Composition modulation of Ag2Te nanowires for tunable electrical and thermal properties.

In this article, we demonstrated that composition modulation of Ag2Te nanowires can be achieved during the self-templated transformation of Te nanowires into Ag2Te nanowires during solution phase synthesis, which provides a mean to tune the carrier density of the Ag2Te nanowires. Both nearly stoichiometric and Ag-rich nanowires have been synthesized, which give rise to p-type and n-type Ag2Te nanocomposites after hot press, respectively. The electrical and thermal properties of the two kinds of samples have been measured. Theoretical modeling based on the near-equilibrium Boltzmann transport equations has been used to understand the experimental results. We found that ZT of the heavily doped n-type sample reaches 0.55 at 400 K, which is the highest ZT value reported for Ag2Te at the same temperature mainly due to the reduced thermal conductivity by the nanostructures. Theoretical analysis on the carrier transport shows that the power factor is also very well optimized in the doped Ag2Te sample considering the reduced carrier mobility by the nanostructures.

Right sizes of nano- and microstructures for high-performance and rigid bulk thermoelectrics.

In this paper, we systematically investigate three different routes of synthesizing 2% Na-doped PbTe after melting the elements: (i) quenching followed by hot-pressing (QH), (ii) annealing followed by hot-pressing, and (iii) quenching and annealing followed by hot-pressing. We found that the thermoelectric figure of merit, zT, strongly depends on the synthesis condition and that its value can be enhanced to ∼ 2.0 at 773 K by optimizing the size distribution of the nanostructures in the material. Based on our theoretical analysis on both electron and thermal transport, this zT enhancement is attributed to the reduction of both the lattice and electronic thermal conductivities; the smallest sizes (2 ∼ 6 nm) of nanostructures in the QH sample are responsible for effectively scattering the wide range of phonon wavelengths to minimize the lattice thermal conductivity to ∼ 0.5 W/m K. The reduced electronic thermal conductivity associated with the suppressed electrical conductivity by nanostructures also helped reduce the total thermal conductivity. In addition to the high zT of the QH sample, the mechanical hardness is higher than the other samples by a factor of around 2 due to the smaller grain sizes. Overall, this paper suggests a guideline on how to achieve high zT and mechanical strength of a thermoelectric material by controlling nano- and microstructures of the material.

Structure and thermoelectric properties of spark plasma sintered ultrathin PbTe nanowires.

Solution-synthesized thermoelectric nanostructured materials have the potential to have lower cost and higher performance than materials synthesized by solid-state methods. Herein we present the synthesis of ultrathin PbTe nanowires, which are compressed by spark plasma sintering at various temperatures in the range of 405-500 °C. The resulting discs possess grains with sizes of 5-30 µm as well as grains with sizes on the order of the original 12 nm diameter PbTe nanowires. This micro- and nanostructure leads to a significantly reduced thermal conductivity compared to bulk PbTe. Careful electron transport analysis shows suppressed electrical conductivity due to increased short-range and ionized defect scatterings, while the Seebeck coefficient remains comparable to the bulk value. The PbTe nanowire samples are found unintentionally p-type doped to hole concentrations of 2.16-2.59 × 10(18) cm(-3). The maximum figure of merit achieved in the unintentionally doped spark plasma sintered PbTe nanowires is 0.33 at 350 K, which is among the highest reported for unintentionally doped PbTe at low temperatures.

Hot carrier filtering in solution processed heterostructures: a paradigm for improving thermoelectric efficiency.

An approach based on a solution-based synthesis that produces a thermally stable Ag/oxide/S2 Te3 -Te metal-semiconductor heterostructure is described. With this approach, a figure of merit of zT = 1.0 at 460 K is achieved, a record for a heterostructured material made using wet chemistry. Combining experiments and theory shows that the large increase in the material's Seebeck coefficient results from hot carrier filtering.

Semimetal/semiconductor nanocomposites for thermoelectrics.

In this work, we present research on semimetal-semiconductor nanocomposites grown by molecular beam epitaxy (MBE) for thermoelectric applications. We study several different III-V semiconductors embedded with semimetallic rare earth-group V (RE-V) compounds, but focus is given here to ErSb:In(x)Ga(1−x)Sb as a promising p-type thermoelectric material. Nanostructures of RE-V compounds are formed and embedded within the III-V semiconductor matrix. By co-doping the nanocomposites with the appropriate dopants, both n-type and p-type materials have been made for thermoelectric applications. The thermoelectric properties have been engineered for enhanced thermoelectric device performance. Segmented thermoelectric power generator modules using 50 µ m thick Er-containing nanocomposites have been fabricated and measured. Research on different rare earth elements for thermoelectrics is discussed.