Engineering thermoelectric and mechanical properties by nanoporosity in calcium cobaltate films from reactions of Ca(OH)2/Co3O4 multilayers.

Controlling nanoporosity to favorably alter multiple properties in layered crystalline inorganic thin films is a challenge. Here, we demonstrate that the thermoelectric and mechanical properties of Ca3Co4O9 films can be engineered through nanoporosity control by annealing multiple Ca(OH)2/Co3O4 reactant bilayers with characteristic bilayer thicknesses (b t ). Our results show that doubling b t , e.g., from 12 to 26 nm, more than triples the average pore size from ∼120 nm to ∼400 nm and increases the pore fraction from 3% to 17.1%. The higher porosity film exhibits not only a 50% higher electrical conductivity of σ ∼ 90 S cm-1 and a high Seebeck coefficient of α ∼ 135 µV K-1, but also a thermal conductivity as low as κ ∼ 0.87 W m-1 K-1. The nanoporous Ca3Co4O9 films exhibit greater mechanical compliance and resilience to bending than the bulk. These results indicate that annealing reactant multilayers with controlled thicknesses is an attractive way to engineer nanoporosity and realize mechanically flexible oxide-based thermoelectric materials.

Atmospheric Water Harvesting by Large-Scale Radiative Cooling Cellulose-Based Fabric.

Atmospheric water harvesting (AWH) has received tremendous interest because of population growth, limited freshwater resources, and water pollution. However, key challenges remain in developing efficient, flexible, and lightweight AWH materials with scalability. Here, we demonstrated a radiative cooling fabric for AWH via its hierarchically structured cellulose network and hybrid sorption-dewing mechanisms. With 8.3% solar absorption and ∼0.9 infrared (IR) emissivity, the material can drop up to 7.5 °C below ambient temperature without energy consumption via radiative cooling. Water adsorption onto the hydrophilic functional groups of cellulose is dominated by sorption at low relative humidity (RH) and dewing at high RH. The cellulose network provides desirable mechanical properties with entangled high-aspect-ratio fibers over tens of adsorption-extraction cycles. In the field test, the cellulose sample exhibited water uptake of 1.29 kg/kg at 80% RH during the night. The profusion of radiative cooling fabric features desirable cost effectiveness and allows fast deployment into large-scale AWH applications.

Thermal conductivity measurements of thin films by non-contact scanning thermal microscopy under ambient conditions.

Thermal conductivity measurements using Scanning Thermal Microscopy (SThM) usually involve heat transfer across the mechanical contact and liquid meniscus between the thermal probe and the sample. However, variations in contact conditions due to capillary effects at probe-sample contact and probe and sample wear due to mechanical contact interfere with accurate determination of the thermal conductivity. This paper presents measurements of thin film thermal conductivity using a SThM method employing a Wollaston probe in non-contact mode in synergy with detailed heat transfer analysis. In this technique, the thermal probe is scanned above the sample at a distance comparable with the mean free path of the ambient gas molecules. A Three-Dimensional Finite Element Model (3DFEM) that includes the specifics of the heat transfer between the sample and the probe in transition heat conduction regime was developed to predict the SThM probe thermal resistance and fit the thermal conductivity of the measured thin films. Proof-of-concept experimental in-plane thermal conductivity results for 240 nm and 46.6 nm Au films deposited on glass and silicon substrates were validated by experimental measurements of their electrical conductivity coupled with the Wiedemann-Franz law, with a discrepancy < 6.4%. Moreover, predictions based on a kinetic theory model for thin-film thermal conductivity agreed with the experimental results for the Au films with <6.6% discrepancy. To reduce the time and complexity of data analysis and facilitate experimental planning, an analytical model was also developed for the thermal transport between the Wollaston probe, ambient, and film-on-substrate samples. The accuracy of thin film thermal conductivity measurements using the analytical model was investigated using 3DFEM simulations. Fitted functions were developed for fast data analysis of thermal conductivity of thin films in the range of ∼100-600 W m-1 K-1 and thickness between ∼50-300 nm deposited on the two types of substrates investigated in this work, which yielded results with a discrepancy of 6-16.7% when compared to the Au films' thermal conductivity values.

Quantitative temperature distribution measurements by non-contact scanning thermal microscopy using Wollaston probes under ambient conditions.

Temperature measurement using Scanning Thermal Microscopy (SThM) usually involves heat transfer across the mechanical contact and liquid meniscus between the thermometer probe and the sample. Variations in contact conditions due to capillary effects at sample-probe contact and wear and tear of the probe and sample interfere with the accurate determination of the sample surface temperature. This paper presents a method for quantitative temperature sensing using SThM in noncontact mode. In this technique, the thermal probe is scanned above the sample at a distance comparable with the mean free path of ambient gas molecules. A Three-Dimensional Finite Element Model (3DFEM) that includes the details of the heat transfer between the sample and the probe in the diffusive and transition heat conduction regimes was found to accurately simulate the temperature profiles measured using a Wollaston thermal probe setup. In order to simplify the data reduction for the local sample temperature, analytical models were developed for noncontact measurements using Wollaston probes. Two calibration strategies (active calibration and passive calibration) for the sample-probe thermal exchange parameters are presented. Both calibration methods use sample-probe thermal exchange resistance correlations developed using the 3DFEM to accurately capture effects due to sample-probe gap geometry and the thermal exchange radii in the diffusive and transition regimes. The analytical data reduction methods were validated by experiments and 3DFEM simulations using microscale heaters deposited on glass and on dielectric films on silicon substrates. Experimental and predicted temperature profiles were independent of the probe-sample clearance in the range of 100-200 nm, where the sample-probe thermal exchange resistance is practically constant. The difference between the SThM determined and actual average microheater temperature rise was between 0.1% and 0.5% when using active calibration on samples with known thermal properties and between ∼1.6% and 3.5% when using passive calibration, which yields robust sample-probe thermal exchange parameters that can be used also on samples with unknown thermal properties.

Quantifying non-contact tip-sample thermal exchange parameters for accurate scanning thermal microscopy with heated microprobes.

Simplified heat-transfer models are widely employed by heated probe scanning thermal microscopy techniques for determining thermal conductivity of test samples. These parameters have generally been assumed to be independent of sample properties; however, there has been little investigation of this assumption in non-contact mode, and the impact calibration procedures have on sample thermal conductivity results has not been explored. However, there has been little investigation of the commonly used assumption that thermal exchange parameters are sample independent in non-contact mode, or of the impact calibration procedures have on sample thermal conductivity results. This article establishes conditions under which quantitative, localized, non-contact measurements using scanning thermal microscopy with heated microprobes may be most accurately performed. The work employs a three-dimensional finite element (3DFE) model validated using experimental results and no fitting parameters, to determine the dependence of a heated microprobe thermal resistance as a function of sample thermal conductivity at several values of probe-to-sample clearance. The two unknown thermal exchange parameters were determined by fitting the 3DFE simulated probe thermal resistance with the predictions of a simplified probe heat transfer model, for two samples with different thermal conductivities. This calibration procedure known in experiments as the intersection method was simulated for sample thermal conductivities in the range of 0.1-50 W m-1 K-1 and clearance values in the 260-1010 nm range. For a typical Wollaston wire microprobe geometry as simulated here, both the thermal exchange radius and thermal contact resistance were found to increase with the sample thermal conductivity in the low thermal conductivity range while they remained approximately constant for thermal conductivities >1 W m-1 K-1, with similar trends reported for all clearance values investigated. It is shown that versatile sets of calibration samples for the intersection method should employ either medium range (1 W m-1 K-1) and (2 W m-1 K-1) thermal conductivities, or wide range (0.5 W m-1 K-1) and (50 W m-1 K-1). The medium range yielded results within 1.5%-20.4% of the expected values of thermal conductivity for specimens with thermal conductivity within 0.1-10 W m-1 K-1, while the wide range yielded values within 0.5%-19.4% in the same range.

Pressure-induced insulator-to-metal transitions for enhancing thermoelectric power factor in bismuth telluride-based alloys.

First-principles calculations revealing insulator-to-metal transitions in Bi2Te3 and Bi2Te2Se, at 9 GPa and 12.5 GPa, respectively, match with prior experiments. Our electronic band structure calculations and accompanying Boltzmann transport calculations of thermoelectric properties for Bi2-xSbxTe2-ySey alloys explain and predict large power factor changes induced by pressure. Complex band degeneracy changes preceding insulator-to-metal transitions significantly alter the density of states near the Fermi level, and foster the disentangling of the unfavorable coupling between Seebeck coefficient and electrical conductivity. Our findings on pressure-induced changes in thermoelectric power factor provide insights for designing V2VI3-based high-performance thermoelectric materials through strategies such as alloying, high-pressure processing, and strain engineering.

Multifold Electrical Conductance Enhancements at Metal-Bismuth Telluride Interfaces Modified Using an Organosilane Monolayer.

Controlling electrical transport across metal-thermoelectric interfaces is key to realizing high efficiency devices for solid state refrigeration and waste-heat harvesting. We obtain up to 17-fold increases in electrical contact conductivity Σc by inserting a mercaptan-terminated organosilane monolayer at Cu-Bi2Te3 and Ni-Bi2Te3 interfaces, yielding similar Σc for both metals by offsetting an otherwise 7-fold difference. The Σc improvements are underpinned by silane-moiety-induced inhibition of Cu diffusion, promotion of high-conductivity interfacial nickel telluride formation, and mercaptan-induced reduction of Bi2Te3 surface oxides. Our findings should enable incorporating nanomolecular layers with appropriately chosen terminal moieties in thermoelectric device metallization schemes without metal diffusion barriers.

Harnessing Topological Band Effects in Bismuth Telluride Selenide for Large Enhancements in Thermoelectric Properties through Isovalent Doping.

Dilute isovalent sulfur doping simultaneously increases electrical conductivity and Seebeck coefficient in Bi2 Te2 Se nanoplates, and bulk pellets made from them. This unusual trend at high electron concentrations is underpinned by multifold increases in electron effective mass attributable to sulfur-induced band topology effects, providing a new way for accessing a high thermoelectric figure-of-merit in topological-insulator-based nanomaterials through doping.

Microwave synthesis of branched silver nanowires and their use as fillers for high thermal conductivity polymer composites.

We report a rapid synthesis approach to obtain branched Ag nanowires by microwave-stimulated polyvinylpyrrolidone-directed polyol-reduction of silver nitrate. Microwave exposure results in micrometer-long nanowires passivated with polyvinylpyrrolidone. Cooling the reaction mixture by interrupting microwave exposure promotes nanocrystal nucleation at low-surfactant coverage sites. The nascent nuclei grow into nanowire branches upon further microwave exposure. Dispersions of low fractions of the branched nanowires in polydimethylsiloxane yield up to 60% higher thermal conductivity than that obtained using unbranched nanowire fillers. Our findings should be useful for realizing nanocomposites with tailored thermal transport properties for applications.

Tailoring Electrical Transport Across Metal-Thermoelectric Interfaces Using a Nanomolecular Monolayer.

We report a 13-fold increase in electrical contact conductivity Σc upon introducing a 1,8-octanedithiol (ODT) monolayer at Cu-Bi2Te3 interfaces. In contrast introducing ODT at Ni-Bi2Te3 interfaces results in a 20% decrease in Σc. Rutherford backscattering spectrometry, X-ray diffraction and electron spectroscopy analyses indicate that metal-sulfur and sulfur-Bi2Te3 bonds at metal-Bi2Te3 interfaces inhibit chemical mixing, curtail metal-telluride formation, and suppress oxidation. Suppressing p-type Cu2Te favors electrical transport across Cu-metallized n-type Bi2Te3, whereas inhibiting the formation of Ohmic-contact-promoting NixTey compromises the electrical conductance at Ni-Bi2Te3 interfaces. Our findings illustrate that molecular nanolayers could be attractive for manipulating interface chemistry and phase formation for tailoring electrical transport across metal-thermoelectric interfaces for solid-state refrigeration applications.

Anisotropic Effects on the Thermoelectric Properties of Highly Oriented Electrodeposited Bi2Te3 Films.

Highly oriented [1 1 0] Bi2Te3 films were obtained by pulsed electrodeposition. The structure, composition, and morphology of these films were characterized. The thermoelectric figure of merit (zT), both parallel and perpendicular to the substrate surface, were determined by measuring the Seebeck coefficient, electrical conductivity, and thermal conductivity in each direction. At 300 K, the in-plane and out-of-plane figure of merits of these Bi2Te3 films were (5.6 ± 1.2)·10(-2) and (10.4 ± 2.6)·10(-2), respectively.

Thermal conductivity measurements of high and low thermal conductivity films using a scanning hot probe method in the 3ω mode and novel calibration strategies.

This work discusses measurement of thermal conductivity (k) of films using a scanning hot probe method in the 3ω mode and investigates the calibration of thermal contact parameters, specifically the thermal contact resistance (R(th)C) and thermal exchange radius (b) using reference samples with different thermal conductivities. R(th)C and b were found to have constant values (with b = 2.8 ± 0.3 µm and R(th)C = 44,927 ± 7820 K W(-1)) for samples with thermal conductivity values ranging from 0.36 W K(-1) m(-1) to 1.1 W K(-1) m(-1). An independent strategy for the calibration of contact parameters was developed and validated for samples in this range of thermal conductivity, using a reference sample with a previously measured Seebeck coefficient and thermal conductivity. The results were found to agree with the calibration performed using multiple samples of known thermal conductivity between 0.36 and 1.1 W K(-1) m(-1). However, for samples in the range between 16.2 W K(-1) m(-1) and 53.7 W K(-1) m(-1), calibration experiments showed the contact parameters to have considerably different values: R(th)C = 40,191 ± 1532 K W(-1) and b = 428 ± 24 nm. Finally, this work demonstrates that using these calibration procedures, measurements of both highly conductive and thermally insulating films on substrates can be performed, as the measured values obtained were within 1-20% (for low k) and 5-31% (for high k) of independent measurements and/or literature reports. Thermal conductivity results are presented for a SiGe film on a glass substrate, Te film on a glass substrate, polymer films (doped with Fe nano-particles and undoped) on a glass substrate, and Au film on a Si substrate.

Correction: Decrease in thermal conductivity in polymeric P3HT nanowires by size-reduction induced by crystal orientation: new approaches towards thermal transport engineering of organic materials.

Correction for 'Decrease in thermal conductivity in polymeric P3HT nanowires by size-reduction induced by crystal orientation: new approaches towards thermal transport engineering of organic materials' by Miguel Muñoz Rojo et al., Nanoscale, 2014, 6, 7858-7865.

Controlling directed self-assembly of gold nanorods in patterned PS-b-PMMA thin films.

We present a facile strategy for the directed self-assembly of gold nanorods (AuNRs) in patterned block copolymer (BCP) thin films. Parallel arrangement of AuNRs relative to the geometric confinement generated by selective removal of one block domain was achieved. Deposition of AuNRs with aspect ratios from 3.3 to 5.8 was accomplished and the alignment of the NRs within the channels was controlled primarily by capillary forces and the channel geometry. Ordered AuNR assembly in the BCP pattern can be achieved at high surface coverages, >30%, though the surface coverage depends on the aspect ratio of the NRs. Larger NRs align in the channels more readily, but pack at slightly lower densities.

Decrease in thermal conductivity in polymeric P3HT nanowires by size-reduction induced by crystal orientation: new approaches towards thermal transport engineering of organic materials.

To date, there is no experimental characterization of thermal conductivity of semiconductor polymeric individual nanowires embedded in a matrix. This work reports on scanning thermal microscopy measurements in a 3ω configuration to determine how the thermal conductivity of individual nanowires made of a model conjugated polymer (P3HT) is modified when decreasing their diameters. We observe a reduction of thermal conductivity, from λNW = 2.29 ± 0.15 W K(-1) m(-1) to λNW = 0.5 ± 0.24 W K(-1) m(-1), when the diameter of nanowires is reduced from 350 nm to 120 nm, which correlates with the polymer crystal orientation measured by WAXS. Through this work, the foundations for future polymer thermal transport engineering are presented.

Large-area freestanding graphene paper for superior thermal management.

Large-area freestanding graphene papers (GPs) are fabricated by electrospray deposition integrated with a continuous roll-to-roll process. Upon mechanical compaction and thermal annealing, GPs can achieve a thermal conductivity of as high as 1238.3-1434 W m(-1) K(-1) . The super-thermally conductive GPs display an outstanding heat-spread ability and are more efficient in removing hot spots than Cu and Al foils.

Self-constructed tree-shape high thermal conductivity nanosilver networks in epoxy.

We report the formation of high aspect ratio nanoscale tree-shape silver networks in epoxy, at low temperatures (<150 °C) and atmospheric pressures, that are correlated to a ∼200 fold enhancement of thermal conductivity (κ) of the nanocomposite compared to the polymer matrix. The networks form through a three-step process comprising of self-assembly by diffusion limited aggregation of polyvinylpyrrolidone (PVP) coated nanoparticles, removal of PVP coating from the surface, and sintering of silver nanoparticles in high aspect ratio networked structures. Controlling self-assembly and sintering by carefully designed multistep temperature and time processing leads to κ of our silver nanocomposites that are up to 300% of the present state of the art polymer nanocomposites at similar volume fractions. Our investigation of the κ enhancements enabled by tree-shaped network nanocomposites provides a basis for the development of new polymer nanocomposites for thermal transport and storage applications.

Seebeck and figure of merit enhancement in nanostructured antimony telluride by antisite defect suppression through sulfur doping.

Antimony telluride has a low thermoelectric figure of merit (ZT < ∼0.3) because of a low Seebeck coefficient α arising from high degenerate hole concentrations generated by antimony antisite defects. Here, we mitigate this key problem by suppressing antisite defect formation using subatomic percent sulfur doping. The resultant 10-25% higher α in bulk nanocrystalline antimony telluride leads to ZT ∼ 0.95 at 423 K, which is superior to the best non-nanostructured antimony telluride alloys. Density functional theory calculations indicate that sulfur increases the antisite formation activation energy and presage further improvements leading to ZT ∼ 2 through optimized doping. Our findings are promising for designing novel thermoelectric materials for refrigeration, waste heat recovery, and solar thermal applications.

A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly.

Obtaining thermoelectric materials with high figure of merit ZT is an exacting challenge because it requires the independent control of electrical conductivity, thermal conductivity and Seebeck coefficient, which are often unfavourably coupled. Recent works have devised strategies based on nanostructuring and alloying to address this challenge in thin films, and to obtain bulk p-type alloys with ZT>1. Here, we demonstrate a new class of both p- and n-type bulk nanomaterials with room-temperature ZT as high as 1.1 using a combination of sub-atomic-per-cent doping and nanostructuring. Our nanomaterials were fabricated by bottom-up assembly of sulphur-doped pnictogen chalcogenide nanoplates sculpted by a scalable microwave-stimulated wet-chemical method. Bulk nanomaterials from single-component assemblies or nanoplate mixtures of different materials exhibit 25-250% higher ZT than their non-nanostructured bulk counterparts and state-of-the-art alloys. Adapting our synthesis and assembly approach should enable nanobulk thermoelectrics with further increases in ZT for transforming thermoelectric refrigeration and power harvesting technologies.

A noncontact thermal microprobe for local thermal conductivity measurement.

We demonstrate a noncontact thermal microprobe technique for measuring the thermal conductivity κ with ∼3 µm lateral spatial resolution by exploiting quasiballistic air conduction across a 10-100 nm air gap between a joule-heated microprobe and the sample. The thermal conductivity is extracted from the measured effective thermal resistance of the microprobe and the tip-sample thermal contact conductance and radius in the quasiballistic regime determined by calibration on reference samples using a heat transfer model. Our κ values are within 5%-10% of that measured by standard steady-state methods and theoretical predictions for nanostructured bulk and thin film assemblies of pnictogen chalcogenides. Noncontact thermal microprobing demonstrated here mitigates the strong dependence of tip-sample heat transfer on sample surface chemistry and topography inherent in contact methods, and allows the thermal characterization of a wide range of nanomaterials.