Symposium QN05 : Emerging Thermal Materials—From Nanoscale to Multiscale Thermal Transport, Energy Conversion, Storage and Thermal Management

Nanomaterials introduce new opportunities in tuning the thermal transport for various applications. Among various nanostructured materials, phonon transport within periodicnanoporous materials has been intensively studied for its potential applications in thermoelectrics, heat waveguides, thermal diodes, and heat imaging.^1,2It is now acknowledged that wave effects of lattice vibrations, i.e., phononic effects, are only important for ultrafine nanoporous structures and at cryogenic temperatures. Experimental evidence is usually found by comparing the thermal conductivities of periodic and aperiodic nanoporous Si films,^3,4or by measuring the specific heat to justify the phonon dispersion variation.⁵
In this work, a new approach is proposed to validate the wave effects, simply by comparing the thermal conductivity of the same Si thin film with increased number of nanopores. When phononic effects exist, it is anticipated that the thermal resistance can be largely increased from single to multiple rows of nanopores. Without phononic effects, the thermal resistance of a patterned Si film should linearly increase with the number of nanopore rows. The measured thermal conductivities are compared to frequency-dependent phonon Monte Carlo simulations that assumes incoherent phonon transport and diffusive pore-edge and film-surface phonon scattering.

Reference:
1. Maldovan, M. Narrow, Low-Frequency Spectrum and Heat Management by Thermocrystals. Phys. Rev. Lett.110, 025902 (2013).
2. Anufriev, R., Ramiere, A., Maire, J. & Nomura, M., Heat guiding and focusing using ballistic phonon transport in phononic nanostructures. Nature communications8, 15505 (2017).
3. Maire, J., Anufriev, R., Yanagisawa, R., Ramiere, A., Volz, S. & Nomura, M. Heat conduction tuning by wave nature of phonons. Science advances3, e1700027 (2017).
4. Lee, J., Lee, W., Wehmeyer, G., Dhuey, S., Olynick, D. L., Cabrini, S., Dames, C., Urban, J. J. & Yang, P. Investigation of phonon coherence and backscattering using silicon nanomeshes. Nature communications8, 14054 (2017).
5. Hao, Q., Xu, D., Zhao, H., Xiao, Y. & Medina, F. J., Thermal Studies of Nanoporous Si Films with Pitches on the Order of 100 nm —Comparison between Different Pore-Drilling Techniques. Scientific Reports8, 9056 (2018).

Thermal storage offers the potential to reduce the amount of waste heat generated by thermal processes and improve overall energy efficiency. Thermochemical storage using reversible reactions has shown considerable potential for high energy density. However, most current thermochemical systems involve the use of at least one gas phase, thus requiring large volumes and reducing energy density. Condensed-phase, particularly all-liquid, thermochemical storage systems are thus highly desirable in order to improve energy density. In this study, we present a computational search for all-liquid thermochemical storage materials based on the Diels-Alder [4+2] cycloaddition reactions. Using high-throughput density functional theory (DFT) calculations, we determined the enthalpy change △H_rxn, entropy change △S_rxn, and turning temperature (T* = △H_rxn / △S_rxn) of 54 Diels-Alder reactions that had been performed in an aqueous solvent in the literature. We screened this test set for turning temperature, identifying nine reactions with a turning temperature close to the working temperature range of water (-50 - 150 degrees Celsius). Several of these reactions (the exo-reaction between furan and maleimide and the reaction between furan and acrylonitrile) were selectively modified using functional group substitution to generate additional reactions for study. These modified reactions were predicted to display exceptional thermal properties, increasing the heat capacity of water by as much as 58.7% and improving the thermal energy density of water by as much as 33.8%. Gravimetric energy densities as high as 0.5598 MJ/kg were predicted. Experimental work to verify the predicted properties of Diels-Alder reactions are ongoing.

Coherent wave effects of thermal phonons hold promise of transformative opportunities in thermal transport control, but remain largely unexplored due to the small wavelength of thermal phonons, typically below a few nanometers. This small length scale indicates that, instead of artificial phononic crystals, a more promising direction is to examine the coherent phonon effects in natural materials with hierarchical superstructures matching the thermal phonon wavelength. In this work, we characterize the thermal properties of dodecagraphene (D-[BL1] graphene), a previously unstudied two-dimensional carbon allotrope based upon the traditional graphene structure but containing a secondary, in-plane periodicity. We use density functional theory (DFT) to calculate harmonic and anharmonic interatomic force constants (IFCs), which were then used to calculate the phonon dispersion, scattering rates, group velocities, and lattice thermal conductivity via an iterative solution to the linearized Boltzmann Transport Equation (BTE). We find that despite a very similar atomic structure, D-graphene possesses significantly different thermal properties than that of pristine graphene. At room temperature the calculated thermal conductivity of D-graphene is 600 Wm^-1K^-1 compared to 3000 Wm^-1K^-1 for graphene. The out of plane acoustic (ZA) mode contribution decreases from 84% in graphene to 47% in D-graphene. We also reportattribute these distinct properties to the presence of three naturally occurring, low frequency optical phonon modes that possess characteristics of phonon coherence and arise from a folding of the acoustic modes and the associated frequency gap opening, a phenomenon also found in superlattices where an out of plane periodicity is introduced. The optical modes make a significant contribution to the thermal conductivity due to enhanced dispersion, comprising over 18% of the thermal conductivity, while the three coherent branches contribute 9% of the total conductivity. The construction of the D-graphene unit cell presents a new method with which the thermal conductivity of 2D materials can be reduced without making drastic changes to its fundamental composition and demonstrates the potential of using coherent phonon effects to significantly modify thermal transport. This work is supported by a Department of Energy Early Career Research Program under award number DE-SC0019244.

The heterogeneities such as defects and dopants can give rise to exotic electronic properties in 2D transition metal dichalcogenides (TMDs), but to this date, there is no detailed study to illustrate how heterogeneities can be engineered to tailor their thermal properties. Here, through combined experimental and theoretical approaches, we have explored the effect of defects, doping, and metal isotopes on the thermal transport of monolayer 2D TMDs grown by chemical vapor deposition (CVD). We found that doping and defects in a CVD-grown monolayers 2D crystals can significantly affect their thermal conductivity due to the mass induced kinetic energy and potential energy difference. Furthermore, we find the isotopically pure monolayer 2D crystals synthesized by CVD can significantly boost their in-plane thermal conductivity resulting from combined effects of the reduced isotope disorder and a reduction in defect-related scattering. Our work demonstrates that heterogeneity engineering can effectively tune the thermal conductivity of 2D TMDs, which is important for thermal properties development and thermal management in 2D electronic and optoelectronic building blocks.

Synthesis science was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division. Characterizations were performed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Efficient thermal insulation using materials with a small environmental footprint is essential for sustainable thermal management in buildings. Nanocellulose produced from wood cellulose fibers is a nanosized, renewable, light weight cellulose particle of high aspect ratio which exhibits tunable surface properties and low thermal conductivity¹. We have previously shown that anisotropic nanocellulose foams prepared by directional freezing exhibit lower thermal conductivity than air (=25 mW/mK) perpendicular to the fibers direction at room temperature².
Here, we will present the heat transfer of anisotropic nanocellulose foams as a function of relative humidity (RH) and temperature (T). Hence, we measure the axial and radial thermal conductivities of anisotropic freeze-casted nanocellulose foams by using a customized hot disk thermal constant analyzer at controlled RH and T. Thermal conductivity measurements have been combined with X-ray diffraction and modelling. The strong dependence of the thermal conductivity on the RH will be related to the interaction of the hygroscopic nanocellulose fibrils with water and humidity-dependence of the directional interfacial thermal resistance. We will also address the effect of the crystallinity and alignment of nanocellulose on the thermal conductivity of anisotropic nanocellulose foams.

References

1. Lavoine, N. & Bergström, L. Nanocellulose-based foams and aerogels: processing, properties, and applications. J. Mater. Chem. A 5, 16105–16117 (2017).
2. Wicklein, B. et al. Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide. Nat. Nanotechnol. 10, 277–283 (2014).

When materials are nanostructured in the 1-100 nm range, fundamental length scales related to transport are often crossed. In the case of heat transport by phonons, the dominant wavelength at room temperature is typically in the 1-10 nm range. Hence, by nanostructuring to this length scale, thermal transport can be modulated in unprecedented ways. Here I will discuss our observations to reduce thermal conductivity below the “alloy limit” as well as reaching the upper limits of phonon conductance. What has eluded the community is the lower limit, which is likely to occur due to Anderson localization. That is the focus of our current work.

The van der Waals, electrostatic or steric forces between liquid molecules and between liquid-solid interfaces fall in the range of 1-10 nm. When liquids are confined to these length scales, they undergo a variety of transitions that control the liquid, ionic and macromolecular transport, as well as liquid-vapor phase transitions. This talk will discuss what we discovered in nanofluidics, which is forming the basis for new research to probe ions, solvation shells and macromolecules in nanofluidic channels.

Finally, I will discuss our current research to use a new class of oxide material for catalysis of a few redox reactions that are important in energy science. This research will also underscore the need for new experimental probes to study catalysis and surface reactions at nanoscales.

The performance of line-focus concentrating solar power (CSP) systems, operating at concentrations <100 suns, is limited by receiver thermal losses. Existing linear CSP receivers rely on spectrally selective surfaces enclosed within cylindrical vacuum tubes to minimize heat loss due to radiation and convection. However, using spectrally selective coatings and maintaining a high-quality vacuum at high temperatures (up to 400 °C) increases cost, reduces durability, and restricts receiver geometry to a cylindrical shape. We have developed a solar thermal aerogel receiver comprising of custom-fabricated highly-transparent thermally-insulating silica aerogels that allow transmission of concentrated sunlight, minimization of thermal losses and enables operation in air. We demonstrate the on-sun performance of the prototype aerogel receiver with a 1 m×10 cm aperture area. The prototype receiver consists of seven monolithic solar-transparent aerogel tiles that cover the solar-absorber consisting of a piping loop connected in series and coated with black Pyromark paint. The receiver is paired with a 6 m×6 m linear Fresnel reflector (LFR) array capable of achieving concentration up to 30 suns. Pressurized Dowtherm A is used as the heat transfer fluid which is heated to temperatures up to 350 °C before entering the receiver section. We performed on-sun measurements for different receiver inlet temperatures and incident flux conditions, and report a peak receiver thermal efficiency >65%.

Concentrated solar power (CSP), also known as high-temperature solar-thermal energy conversion, is a promising solar energy harvesting technology due to its efficient sunlight utilization, and high availability in energy storage. For the sake of higher Carnot efficiency and greater cost reduction, next-generation CSP plants are expected to operate at higher temperatures (≥900 K) than those conventional systems. Selective solar absorbers, as the key components in CSP systems, are required to offer high stability and great selectivity at such high temperatures. Selective solar absorbers based on multilayer metal/ceramic thin films are a kind of low-cost and scalable absorbers fabricated by facile processes such as sputtering deposition. However, their thermal stability and spectral selectivity fall behind those state-of-the-art cermets and photonic absorbers. Previously works demonstrated that multilayer absorbers suffered from a variety of high-temperature degradation cases associated with the metal/ceramic interfaces, including delamination, surface oxidation, and atom diffusion.
In this work, we introduced a TiN IR reflector into the multilayer absorbers to replace refractory metals (W, Ta, Mo, etc.) used in conventional designs; meanwhile, another ceramic material, titanium oxy-nitride (TiNO), was utilized as the absorptive layer due to its tunable absorption properties and excellent compatibility with TiN. Two ceramic anti-reflection layers, ZrO₂ and SiO₂, with gradient refractive indexes were adopted to reduce the surface reflection, and enhance the sunlight absorption. The fabricated all-ceramic absorber displayed highly selective absorption with a high solar absorptance of 91.2% and an ultralow IR emittance of 15.7% at 1000 K. Consequently, a high solar-thermal conversion efficiency of 82.1% was achieved under the irradiation of 100 suns. This value is on par with or exceeds the record of state-of-the-art selective absorbers. As expected, the all-ceramic absorber was able to sustain its superior performance at high temperatures up to 800 °C. Both SEM-EDX and depth profiles of elements results reveal that the diffusion and oxidation were effectively suppressed in the all-ceramic structure. Moreover, the delamination was also avoided in the ceramic/ceramic interfaces. Compared with previous multilayer absorbers, this all-ceramic absorber boosted the operating temperature of such low-cost multilayer absorbers by ~300 °C, rendering it suitable for the high-temperature applications in next-generation CSP plants.

Thermal processes and materials involving phase change, are practically omnipresent in nature and technology. Viewed in the direction of decreasing temperature, the encountered phase transitions are condensation, freezing and de-sublimation. All share significant scientific challenges in terms of material/surface engineering to control nucleation and growth of the generated phase on a surface, and assure its continuous and facile, passive removal from the surface, to maintain surface functionality and robust performance at a high level, depending on the application of interest. Here, I will focus on the rational, physics-derived, surface nanoengineering, for condensation applications, ranging from power generation targeting high efficiency, to sunlight-driven fogging retardation and rapid defogging of transparent materials.

Enhancing the thermal efficiency of a broad range of condenser devices requires means of achieving sustainable dropwise condensation on metallic surfaces, where heat transfer can be further enhanced by facilitating a reduction in the droplet departure diameter. I will present a rationally driven, hierarchical texturing process of metallic surfaces, guided by the collaborative action of wettability and coalescence, which achieves controlled droplet departure, also under challenging vapor flow conditions significantly enhancing heat transport. The textures are attained by both etching processes generating a random but hierarchical re-entrant landscape, as well as by fabricating an array of 3D laser-structured truncated microcones on the surface, covered with papillae-like nanostructures and a hydrolytically stable, low surface energy self-assembled-monolayer coating. Passive droplet departure on this surface is achieved through progressive coalescence of droplets generated and continuously arising from microcavities, resulting in robust depinning and subsequent departure of the condensate, through vapor shear or gravity, Refs. 1,2.

Condensation is also responsible for fogging, a common phenomenon that can have detrimental effects on visibility through otherwise tramnsparent surfaqes. Fogging affects the performance of a wide range of everyday applications including windshields, visors, displays, cameras, and eyeglasses. I will present a novel approach, based on sunlight absorbing metasurfaces, which goes well-beyond state-of-the-art anti-fogging methods such as superhydrophilic coatings. We rationally nanoengineer such transparent metasurfaces, by varying the concentration of embedded plasmonically enhanced light absorbing nanoparticles in an ultra-thin titania film to achieve broadband absorption with tunable transparency. Such surfaces upon illumination induce significant heating at the air-substrate interface where fog is most likely to form and can rapidly de-fog or completely inhibit fog nucleation altogether, Ref. 3. For the same environmental conditions, we demonstrate that such metasurfaces are able to reduce defogging time by up to four-fold compared to reference samples and markedly outperform the most widely implemented solution in anti-fogging, namely, superhydrophilic surfaces. This approach work paves the way for large-scale, low-cost manufacturing that can be applied to a versatile range of materials, including polymers and other flexible substrates, which can further be combined with state-of-the-art technology to overcome remaining impracticalities, safety, and energy-related costs related to fogging.

References:
1. C. S. Sharma, J. Combe, M. Giger, T. Emmerich and D. Poulikakos. ACS Nano, 11 (2): 1673-1682, DOI: 10.1021/acsnano.6b07471
2. C. S. Sharma , C Stamatopoulos, R. Suter, P. Rudolf von Rohr and D. Poulikakos. ACS Appl. Mater. Interfaces, 2018, 10 (34), pp 29127–29135. DOI: 10.1021/acsami.8b09067
3. C. Walker, E. Mitridis, T. Kreiner, H. Eghlidi, T. Schutzius and D. Poulikakos, Transparent Metasurfaces Counteracting Fogging by Harnessing Sunlight, 2018, in review.

I will review several collaborative efforts at developing new non-contact methods for heating and thermometry at the nanometer scale. Examples include techniques based on SEM (e-beam as a point heater; secondary electron yield as a thermometer), TEM (thermometry using the Debye-Waller effect), and confocal microscopy (luminescence thermometry of individual nanoparticles).

Conventionally, the two-temperature model has been widely used for electron-phonon coupled non-equilibrium thermal transport. However, many recent applications have shown that different phonon branches can be in strong thermal non-equilibrium. Therefore, assuming a local equilibrium lattice can lead to misleading or wrong results. Here, we present a multi-temperature model to capture the non-equilibrium among different phonon branches, and demonstrate its advantages over the conventional two-temperature model for bulk materials and across interfaces.

The thermal conductivity of materials is not a fixed physical property but can be manipulated by controlling the transport properties of thermal phonons. Recently, a large number of experiments have been introduced where thermal conduction is reduced by orders of magnitude via phonon mean free path reduction through diffuse surface scattering. In contrast to established work that use the diffuse surface scattering of phonons as the physical mechanism to reduce the thermal conductivities, in this talk we show that the largest reduction of thin film heat conduction is achieved via specular scattering. Our results thus create a new paradigm for heat conduction manipulation since smooth surfaces – in contrast to rough surfaces – can be more effective on suppressing thin film phonon heat conduction.

Effect of structural disorder on phonon thermal conduction remains an open question with a large spectrum of physical effects, as the plane-wave description of atomic vibrations is expected to become irrelevant. In a first stage, atomic scale disorder will be investigated in various systems –silicon [1], SiGe nanowires [2], partial-crystal partial-liquid [3], 2D [4,5] - with atomic scale simulations. Secondly, thermal properties of nanoscale random materials [6,7] will be presented to raise the question of the eventual impact of localization on heat conduction.

[1] K. Sääskilahti, J. Oksanen, J. Tulkki, A. J. H. McGaughey, and S. Volz, Vibrational mean free paths and thermal conductivity of amorphous silicon from non-equilibrium molecular dynamics simulations, AIP Advances.
[2] Honggang Zhang, Haoxue Han, Shiyun Xiong, Hongyan Wang, Sebastian Volz, and Yuxiang Ni, Impeded thermal transport in composition graded SiGe nanowires, App. Phys. Lett., 111, 121907, (2017).
[3] Y. Zhou, S. Xiong, X.L. Zhang, S. Volz, M. Hu, Thermal Transport Crossover from Crystalline to Partial-crystalline Partial-liquid State, Nat. Comm., accepted.
[4] Van-Truong Tran, Jérôme Saint-Martin, Philippe Dollfus & Sebastian Volz, Optimizing the thermoelectric performance of graphene nano- ribbons without degrading the electronic properties, Sc. Rep., 7: 2313 | DOI:10.1038/s41598-017-02230-0.
[5] Van-Truong Tran, Jérôme Saint-Martin, Philippe Dollfus and Sebastian Volz, High thermoelectric performance of graphite nanofibers, Nanoscale, DOI: 10.1039/C7NR07817J
[6] J. Maire, R. Anufriev, R. Yanagisawa, A. Ramiere, S. Volz, and M. Nomura, Heat conduction tuning by wave nature of phonons, Science Advances, 3(8), e1700027 (2017).
[7] S Hu, Z Zhang, P Jiang, J Chen, S Volz, M Nomura, B Li, Randomness-Induced Phonon Localization in Graphene Heat Conduction, The journal of physical chemistry letters 9 (14), 3959-3968

Polymers have entered almost every aspect of modern life, from packaging and soft robotics to aerospace sector and 3D printing. Traditional polymers are both electrically and thermally insulating. The discovery and development of electrically conductive polymers has led to innovative electronic applications such as flexible displays, wearable biosensors and lightweight photovoltaics. As in the case of electrically conductive polymers, the development of thermally conductive polymers would open up a range of advanced thermal applications including an emerging self-cooling system to existing electronics casings. This talk will summarize our recent work on improving thermal conductivity of polymers. We developed scalable polyethylene films with thermal conductivity ~62 W/m-K by extrusion and roll-to-roll drawing processes . Structural studies and thermal modeling reveal that the film consists of nanofibers with crystalline and amorphous regions, and the amorphous region has a remarkably high thermal conductivity of ~16 W/m-K. We grew thermally conductive conjugated polymer by bottom-up oxidative chemical vapor deposition technique, and realized high thermal conductivity ~2.2 W/m-K in conjugated polymer (P3HT) thin film by engineering both inter- and intramolecular interactions and taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong π-π stacking noncovalent interactions between chains. We will also discuss our current work on enhancing heat conduction in hydrogels. This work is supported by Department of Energy–Basic Energy Sciences under award number DE-FG02-02ER45977.

According to conventional theories of heat conduction in semiconductors and insulators, only crystals composed of strongly-bonded light elements can have high lattice thermal conductivity (k_L), and intrinsic thermal resistance comes only from lowest-order anharmonic three-phonon interactions. Recently, we proposed a new paradigm for achieving high k_L in which the vibrational properties are engineered to reduce the phase space for three-phonon scattering. Some binary compounds with a heavy-light atom combination in the unit cell can achieve the requirements, and first principles calculations for one material, cubic Boron Arsenide (BAs), gave three-phonon limited k_L > 2000 W/m-K at room temperature [2], comparable to that of best heat conductor, diamond. Subsequent calculations [2] showed the importance of higher-order four-phonon scattering in also limiting the k_L in compounds such as BAs but still predicted room temperature values > 1000 W/m-K for BAs, far higher than any other semiconductor, and recent synthesis and measurement efforts [3-5] have confirmed that BAs does indeed have the predicted high k_L. In this talk, I will review the theoretical predictions and the challenging material constraints that must be satisfied in order to achieve the unconventional high k_L, as in BAs. I will discuss one set of candidate compounds we have examined – group V transition metal carbides – that have ideal vibrational properties similar to BAs but are metals with nested Fermi surfaces. This gives rise to an unusual combination of the desired weak phonon-phonon scattering but strong phonon-electron scattering and results in low k_L that is nearly temperature independent, contrary to the typical behavior in metals.

D.B. acknowledges support from the Office of Naval Research MURI, Grant No. N00014-16-1-2436.

[1] L. Lindsay, D. A. Broido, and T. L. Reinecke, Phys. Rev. Lett. 111, 025901 (2013).
[2] T. Feng, L. Lindsay, and X. Ruan, Phys. Rev. B, 96, 161201 (2017).
[3] J. S. Kang M. Li, H. Wu, H Nguyen, and Y. Hu., Science 361, 575 (2018).
[4] S. Li, Q. Zheng, Y. Lv, X. Liu, X. Wang, P. Y. Huang, D. G. Cahill, and B. Lv, Science 361, 579 (2018).
[5] F. Tian et al., Science 361, 582 (2018).
[6] C. Li, N. K. Ravichandran, L. Lindsay, and D. Broido, Phys. Rev. Lett. 121, 175901 (2018).

Optical phonon linewidth is crucial to infrared dielectric function of polar materials and thermal conductivity of certain materials that have a large number of optical phonon branches. The current understanding of optical phonon linewidth is associated with three-phonon scattering. In this work, however, we show that four-phonon can dominate the optical phonon linewidth and infrared optical properties at elevated temperatures for a range of important materials, including cubic boron arsenide (BAs), cubic silicon carbide (3C-SiC), and α-quartz. Strikingly, in large band gap-materials, e.g., BAs and AlSb, four-phonon scattering rates are found to be orders of magnitude higher than three-phonon scattering rates even at room temperature. The predicted infrared optical properties of α-quartz after including four-phonon scattering can well explain experimental measurements.

Heat dissipation has become an increasingly important technological challenge in modern electronics. Discovering new high thermal conductivity materials that can efficiently dissipate heat from hot spots and improve device performance are urgently needed. In this talk, I will describe our recent progress in developing emerging high thermal conductivity semiconductors including boron arsenide (BAs) and boron phosphide (BP). We synthesized BAs and BP single crystals without detectable defects, and measured a room temperature thermal conductivity of 1300 W/mK [1] and 500 W/mK [2] respectively. Our ultrafast spectroscopy study in conjunction with atomistic theory reveals that the unique band structure of BAs allows for very long phonon mean free paths and strong high-order anharmonicity through the four-phonon process. The single-crystal BAs has the highest thermal properties among all common metals and semiconductors. In addition, I will briefly discuss our efforts in characterizing thermal boundary resistance and integrating BAs and BP with high-power electronics for near-junction thermal management applications through the combination of measurement and atomistic simulations. Our study establishes BAs and BP as new benchmark materials for thermal management applications, and exemplifies the power of combining experiments and ab initio theory in new materials discovery.

References:
1. Joon Sang Kang, Man Li, Huan Wu, Huuduy Nguyen, and Yongjie Hu, “Experimental observation of high thermal conductivity in boron arsenide,” Science 361, 575-578 (2018).
2. Joon Sang Kang, Huan Wu, and Yongjie Hu, “Thermal Properties and Phonon Spectral Characterization of Synthetic Boron Phosphide for High Thermal Conductivity Applications,” Nano Letters 17, 7507 (2017).

Thermal management is critical for electronic systems ranging from servers and smartphones to radar HEMTs and hybrid vehicle conversion devices. Much progress is being achieved by leveraging nanofabrication strategies from the electronics, photonics, and materials science communities for heat transfer structures and systems, which have been limited by more traditional methods of synthesis. One example is the template-fabrication of metal inverse opals for application as porous media for phase change heat transfer. This fabrication methodology offers very systematic pore shapes and distributions, down to a few micrometers, and facilitates breakthrough combinations of high fluidic permeability and high solid thermal conductivity (1,2). We have shown that inverse opals can be conformally coated onto microchannel walls in silicon and diamond microfluidic heat sinks, thereby facilitating solid-state heat conduction spreading with liquid and vapor phase routing and management in the heat sink (3). We have also shown recently that controlled sintering of the templates before electrodeposition can be used to modify the dimensions of the “necks” or hydraulic vias between adjacent pores and augment the permeability with modest reductions in the effective thermal conductivity, which is an important result for wick engineering in capillary-based devices (4). Our simulations and experiments have explored the impacts of wick dimensions and structure on the suppression and ultimate onset of boiling crisis, as well as the reduction of superheat values for heat fluxes well above 1 kW/cm2 (5). This talk will highlight both our fundamental simulations and experiments on inverse-opal based wicks and microfluidic heat sinks, as well as our efforts to bring these technologies to our collaborations with the semiconductor industry, with US defense companies, and within the NSF center on power electronics (POETS).

(1) Zhang, Palko, Barako, Asheghi, Santiago, Goodson, 2018, "Enhanced Capillary Fed Boiling in Copper Inverse Opals via Template Sintering,” Advanced Functional Materials 1803689.

(2) Barako, Sood, Zhang, Wang, Kodama, Asheghi, Zheng, Braun, Goodson, 2016, “Quasi Ballistic Electronic Thermal Conduction in Metal Inverse Opals,” Nano Letters, Vol. 16, pp. 2754-2761.

(3) Palko, Won, Agonafer, Resler, Altman, Asheghi, Santiago, Goodson, et al., 2017, “Extreme Two Phase Cooling from Laser Etched Diamond and Conformal, Template Fabricated Microporous Copper,” Advanced Functional Materials, Vol. 27, 1703265.

(4) Zhang, Palko, Pringle, Barako, Asheghi, Santiago, Goodson, et al., 2018. "Tailoring permeability of microporous copper structures through template sintering,” ACS Applied Materials & Interfaces.

(5) Palko, Zhang, Asheghi, M., Goodson, Santiago, et al., 2015, "Approaching the Limits of Two Phase Boiling Heat Transfer: High Heat Flux and Low Superheat," Applied Physics Letters, Vol. 107, 253903.

Condensation and boiling are integral processes in many industrial applications including power generation, HVAC, and thermal management of electronic systems. Current efforts aimed at increasing heat transfer during these processes predominantly focus on altering either the chemistry or the texture of the solid-fluid interface. In this talk we will expand beyond these two design variables and will discuss how softening of these surfaces impacts dropwise condensation [1] and nucleate boiling [2]. An intriguing component of these phase change processes on soft surfaces is that both microscale droplets and bubbles can significantly deform such materials through Laplace pressure and capillary force at the triple phase contact line. We first discuss how these elastocapillary processes impact heat transfer during condensation across individual droplets as well as their nucleation, growth, and shedding. By integrating these trends over droplet population, we show that softening of the surfaces below shear modulus of about 500 kPa is detrimental to dropwise condensation. In contrast, we use theoretical arguments to show that softening of the surface could significantly facilitate onset of nucleate boiling (ONB). Specifically, we use classical kinetic theory to show that softening of a smooth-surface could mildly decrease superheat needed for ONB. We also discuss a close-form model of vapor trapping and bubble seeding from soft surfaces with conical cavities to show that superheat needed for ONB decreases linearly with shear modulus of the surface. Thus, our work shows that boiling could be manipulated using mechanical properties of the surface. We will also briefly discuss practicalities involved in implementing soft surfaces in boilers and some of the remaining outstanding fundamental questions.

[1] A. Phadnis and K. Rykaczewski, Langmuir, 33, (43), 12095-12101, 2017.
[2] K. Rykaczewski and A. Phadnis, Nanoscale and Microscale Thermophysical Engineering, 22, 3, 2018.

A novel solar heating (SH) and radiative cooling (RC) system based on black surface with selective cover (BS-S) is proposed. This system can provide heat via photothermal conversion and obtain cooling energy by radiative cooling. Photonic approach is applied to design selective cover for SH-RC system. The selective rigid cover consists of a 500 μm-thick zinc sulfide (ZnS) substrate and alternating layers of ZnS and ytterbium fluoride (YbF₃) with varying thicknesses. It has strong and remarkably spectral selective characteristics. The transmissivity in SH band (i.e., 0.3–2.5 μm) and RC band (i.e., 8–13 μm) is approximately 0.85, the reflectivity in wavelength band 3–8 μm is approximately 0.70. With the selective rigid cover, air pressure between the cover and black surface could be low (maybe even vacuum) to suppress heat conduction and heat conduction. Numerical analysis demonstrates that in SH process, when surface temperature is 80 °C, the vacuum BS-S case shows a thermal efficiency of 45.9%, approximately 11.5% higher than that of the typical air pocket BS-S case. In RC process, the equilibrium temperature of the vacuum BS-S case and the typical air pocket BS-S case are lower than those of ambient air by approximately 28.9 °C and 22.5 °C, respectively. This selective rigid cover provides an alternative choice for integrating combined SH-RC system and has potential to enhance the performance of the diurnal solar heating and nocturnal radiative cooling processes.

Liquid-vapor phase change is essential in many applications including water purification, power generation, and thermal management. However, effectively utilizing these processes requires detailed understanding and manipulation of interfacial transport. In the first part of the talk, we discuss evaporation from ultra-thin nanoporous membranes. Fundamental understanding during evaporation remains limited to date as it is generally challenging to characterize the heat and mass transfer at the interface, particularly when the heat flux is high (>100 W/cm²). We fabricated ultra-thin (≈ 200 nm thickness) nanoporous (≈ 130 nm pore diameter) membrane devices which reduced the thermal-fluidic transport resistance and accurately monitored the temperature of the liquid-vapor interface. We showed that kinetically limited evaporation, when normalized properly, is solely determined by the pressure ratio between the ambient and the interface. We modeled the gas kinetics and demonstrated good agreement between experiments and theory. Our work provides a general figure of merit for evaporative heat transfer as well as design guidelines for achieving efficient evaporation. In the second part of the talk, we show a nanostructured surface that can repel liquids even during condensation. This surface consists of isolated reentrant cavities with a pitch on the order of 100 nanometers to prevent droplets from nucleating and spreading within all structures. We developed a model to guide surface design, and subsequently fabricated and tested these surfaces with various liquids. We demonstrated repellency to various liquids up to 10 °C below the dew point and showed durability over three weeks. These works provide insights into nanostructured designs for enhanced phase change heat transfer.

Continuum-scale simulations of phase change processes are essential for assisting the design of engineering systems, such as heat pipes and combustion chambers. To quantitatively predict the rate of the phase change in micro-scale systems it is imperative to properly account for the boundary conditions at the interface between phases. For example, in liquid-vapor phase change simulations, the typical continuum assumptions are, a) temperature is continuous at the interface, and b) vapor density near the interface is equal to the saturated density. Results of molecular dynamics (MD) simulations have indicated that in many situations such assumptions are not satisfied. To address these issues, we present a framework for continuum simulations capable of relaxing the aforementioned assumptions. We use finite elements to solve the Navier-Stokes equations while correctly accounting for the flux jump conditions at the interface. Expressions for phase change rates and temperature jumps are obtained from theoretical considerations and augmented by MD simulations. Problems including the burning of solid propellants and evaporation/condensation of liquids are discussed.

Solar thermophotovoltaic (STPV) systems, which leverage the benefits of both solar-thermal and photovoltaic (PV) technologies, involve efficient and dispatchable approaches to generating electricity. The key components in a STPV system include a selective solar absorber, a selective emitter, and a solar cell at least. The total input power of a SPTV system is determined by the sunlight absorption efficiency of the selective absorber. Considering the high operating temperatures of STPV systems, selective absorbers are required to maintain high absorption for solar radiation and low emission beyond a cut-off wavelength in the infrared region to avoid thermal re-radiation even at elevated temperatures. To date, almost all the state-of-the-art selective absorbers/emitters such as cermets and photonic crystals with superior performance (i.e., high selectivity and great thermal stability) were generally manufactured with complicated and expensive micro-fabrication or nano-fabrication techniques, leading to high cost and challenges for large-scale production. Moreover, the obtained absorbers/emitters often encounter problems when being integrated with solution-processed solar cells. Therefore, developing high-performance solution-processed absorbers/emitters is urgently demanded.
Titanium nitride (TiN), as an emerging plasmonic ceramic material, offers tunable plasmonic properties, as well as great thermal and chemical stability. TiN nanoparticles have been proven to show stronger optical losses in the visible range compared to traditional metallic plasmonic materials. In this work, we took advantage of well-dispersed colloidal TiN nanoparticles (20-80 nm) to serve as the absorptive medium for sunlight. The absorption bandwidth, i.e., the cut-off wavelength, can be tuned through rationally controlling the concentration of the TiN colloid and the coating speed. The excited plasmonic resonance of TiN nanoparticles resulted in highly selective absorption of sunlight near their resonance wavelengths. Due to the in-plane plasmonic coupling of adjacent TiN nanoparticles, the resonance wavelength was able to red-shift to near-infrared (NIR) range. As a result, selective sunlight absorption can be attained in the UV-visible-NIR range below the cut-off wavelength. An amorphous SiO_x layer, prepared by spin coating a perhydropolysilazane (PHPS) solution, acted as the protection and anti-reflection coating. Both full-spectrum sunlight absorption and strong IR reflection were achieved simultaneously when coated on various IR reflectors, including Au, stainless steel, Al, and TiN. Particularly, the absorbers with Au reflectors exhibited a high solar absorptance of 92.1% and an ultra-low IR emittance of 10.5% at an elevated temperature of 1000 K, producing a solar-thermal energy conversion efficiency of 86.1% under 100 suns. To the best of our knowledge, this performance surpasses or equals those of state-of-the-art selective absorbers fabricated by micro and nano-fabrication techniques. The superior performance of such low-cost solution-processed solar absorbers will potentially put the steps of cost-effective and large-scale STPV systems forward.

The dynamic control of thermal transport properties in solids must contend with the fact that phonons are inherently broad-band. Thus, efforts to create reversible thermal conductivity switches have resulted in only modest on/off ratios, since only a relatively narrow portion of the phononic spectrum is impacted. Here, we report on the ability to modulate the thermal conductivity of topologically networked materials by nearly a factor of four following hydration, through manipulation of the displacement amplitude of atomic vibrations. By varying the network topology, or crosslinked structure, of squid ring teeth-based bio-polymers through tandem-repetition of DNA sequences, we show that this thermal switching ratio can be directly programmed. This on/off ratio in thermal conductivity switching is over a factor of three larger than the current state-of-the-art thermal switch, offering the possibility of engineering thermally conductive biological materials with dynamic responsivity to heat.

Manipulating heat conduction is an appealing thermophysical problem with enormous practical implications, which requires insight into the lattice dynamics. Strain engineering is one of the most promising and effective routes towards continuously tuning the thermal transport properties of materials due to the flexibility and robustness. However, previous studies mainly focused on quantifying how the thermal conductivity is affected by strain, while the fundamental understanding on the electronic origin of why the thermal conductivity can be modulated by mechanical strain has yet to be explored. In this talk, I would like to present our comparative study of thermal transport in two-dimensional group III-nitrides (h-BN, h-AlN, h-GaN) and graphene. Although the monolayer group III-nitrides possess similar planar honeycomb structure with graphene, their thermal conductivity is substantially lower and the root reason cannot be intuitively attributed to the mass difference. We then establish a microscopic picture to connect phonon anharmonicity and lone-pair electrons. Direct evidence is provided for the interaction between lone-pair electrons and bonding electrons of adjacent atoms based on the analysis of orbital-projected electronic structures, which demonstrates how nonlinear restoring forces arise from atomic motions and lead to strong phonon anharmonicity. The microscopic picture of lone-pair electrons driving strong phonon anharmonicity provides coherent understanding of the diverse thermal transport properties of the monolayer group III-nitrides compared to graphene. Furthermore, the thermal conductivity (κ) of planar monolayer group III-nitrides is unexpectedly enlarged by up to one order of magnitude with bilateral tensile strain applied, which is in sharp contrast to the strain induced κ reduction in graphene despite their similar planar honeycomb structure. The anomalous positive response of κ to tensile strain is attributed to the attenuated interaction between the lone-pair s electrons around N atoms and the bonding electrons of neighboring (B/Al/Ga) atoms, which reduces phonon anharmonicity. The microscopic picture for the lone-pair electrons driving phonon anharmonicity established from the fundamental level of electronic structure deepens our understanding of phonon transport in 2D materials and would also have great impact on future research in micro-/nanoscale thermal transport such as materials design with targeted thermal transport properties.

We report the electrothermal properties of AZO/Ag/AZO (AAA) trilayer on PET, which helped us develop a low cost high performance transparent flexible electrode and heater (TFEH) using RF magnetron sputtering. The thickness of the Ag interlayer (1.6 nm to 5 nm) in the AAA trilayer was varied, and its electrical, optical and structural properties was thoroughly investigated. At optimized Ag interlayer thickness of 5 nm, the AAA trilayer based TFEH yielded saturation temperatures beyond 100 °C at 10 V which makes it a suitable energy efficient device. The time dependent temperature profile along with its highly stable and reversible thermal behavior demonstrated that it is a promising low cost TFEH device that can be developed industrially on large areas using RF magnetron sputtering. Most importantly the AAA trilayer based TFEH provides a high-performance alternative to the conventional ITO electrodes at a much lower cost.

We present new composite with significantly improved Thermal Conductivity (TC) that comprises a continuous network of thermally conductive fillers and a natural polyol. The network of thermally conductive filler, in this case boron nitride nanosheets (BNNS), was an aerogel that was fabricated with the ice template method. Subsequently, the aerogel was carbonized and filled with xylitol with help of vacuum infiltration of liquefied xylitol. The aerogel provided a 3D thermal conductive pathway and also acted as a scaffold to promote the oriented crystallization of xylitol. Our results demonstrate that the BNNS scaffold and packing of oriented xylitol crystals play a key role in improving TC of the composite. With BNNS content of 18.16 wt% (6.14 vol %) TC of above 4.5 W/ (m.K), which is higher than that reported in recent literatures, was obtained.

We use molecular dynamics simulations to determine the pressure-induced structural changes in several oxide glasses including permanent densification and the effect of these changes on thermal properties. We show that densified glass structures exhibit increased thermal conductivity, which may be attributed to the increased density and elastic modulus. The local properties analysis reveals that the higher-pressure treatment reduces elastic heterogeneities, which might also contribute to higher thermal conductivity of densified glasses.

Gallium doped zinc oxide (GZO) and Aluminum doped zinc oxide (AZO) thin films were often grown on substrates such as glass, flexible polyethylene terephthalate substrate through using physical vapor deposition technique. The thin films were ultra-smooth in nature and showed outstanding optical, and electrical properties. Highly compact and dense PLD target was made in the laboratory fromAl2O3, Ga2O3 and ZnO powder in an appropriate proportion with a less than 10 atomic weight percentages of Ga and Al followed by isotactic press as well as high temperature annealing (1200 oC) for 12 hours. AZO thin films show stable and reproducible joule heating effect of more than 100oC by the application of low (<10 V) voltages. GZO transparent heater also showed a stable and reproducible Joule heating effect and the temperature can reach easily close to the 100oC by the application of low input 〈8V voltages. The samples showed low resistivity of about 2.6×10⁻⁴ Ω cm and 3.7×10⁻⁴Ω cm and also exhibited high optical transparency value in the visible region of the electromagnetic spectrum. The temperature dependent resistivity behavior of the films were investigated using four-point probe technique. This exciting results encourages the use of GZO and AZO transparent oxide in different optoelectronics device application.

Advances in nanotechnology have contributed to dramatically increasing the thermal conductivity of fluids. Nanoparticles with high thermal conductivity have a high surface area relative to their mass and thus increase the thermal conductivity of the fluid more efficiently with a small amount of addition. However, unlike a pure solution such as DI water, complex fluids such as drilling mud have a large influence of other components so not too much increase the thermal conductivity through the addition of nanoparticles. Therefore, we do not simply add nanoparticles but use a method to increase the thermal conductivity by growing ceramics with high thermal conductivity directly on the solid particle surface added to the complex fluid. Synthesis of nanoparticles using the conventional bottom-up method was inferior in terms of cost and yield compared to synthesizing nanoparticles in a top-down method. But it is expected that only small amounts of nanoparticles will have a great effect, if the particles are synthesized only on the surface of the other particles by the bottom-up method.
We made drilling mud after functionalization of ceramics (BN, SiC, MoS₂, WS₂) with high thermal conductivity on bentonite surface which is the most important additive substance to drilling mud. Thermal conductivity of the drilling mud was compared with the conventional method in which the same amounts of nanoparticles were simply mixed in the conventional method in which the same amounts of nanoparticles were simply mixed in the drilling mud. We also measured the FE-SEM, RAMAN, and XPS to check the growth of the particles on the bentonite surface and measured the viscosity according to the flow rate to confirm the performance as a drilling mud. We report how to increase the thermal conductivity of a complex fluid in a different way than previously.

The exceptionally high thermal conductivity of graphene has driven interest toward its applications in thermal interface materials (TIMs) [1-3]. In addition to its unique heat conduction properties, graphene is also a strong conductor of electricity, which is problematic for certain TIM applications where electrical insulation is paramount. A common strategy for the optimization of composite materials is to combine two or more different thermally conductive fillers. Typically, work along this vein employs fillers of disparate size, shape, and aspect ratios with the larger-sized fillers providing the greatest contribution of overall thermal transport and the smaller fillers improving the interstitial thermal coupling between the larger fillers. Unlike much of the previous work into binary fillers, we report on polymer composites filled with few-layer graphene and hexagonal boron nitride (h-BN) of similar lateral dimensions, thicknesses, and aspect ratios. In each filler material, phonons are the primary heat carrier, necessitating the selection of lateral dimensions larger than the “gray” phonon mean free path (MFP) in the micrometer distance range. The composition and structure of the resulting epoxy-based composites were verified using scanning electron microscopy (SEM), Raman, and Brillouin spectroscopy. Thermal measurements were conducted using the “laser flash” techniques. It was found that the use of electrically conductive graphene and electrically insulating h-BN fillers of similar physical dimensions can be complementarily leveraged to achieve an independent control of the thermal and electrical conductivity of the TIM. Varying the constituent fraction of graphene in composites with ~44% total filler loading can tune the thermal conductivity enhancement from a factor of ×15 to ×34 while changing the electrical resistivity from 3×10⁸ Ω-mm to 10² Ω-mm, i.e. spanning the resistivity range from an insulator to a conductor. We offer an analytical model that describes the experimental thermal conductivity data of the binary filler composites. The obtained results are illustrative of a promising strategy for the development of next-generation thermal interface materials with specific control of electrical properties, allowing for the expression of electrically insulating or electrically grounding behaviors.
This work was supported, in part, by the National Science Foundation (NSF) through the Emerging Frontiers of Research Initiative (EFRI) 2-DARE award 1433395, and by the UC – National Laboratory Collaborative Research and Training Program LFR-17-477237.
[1] A.A. Balandin, Thermal properties of graphene and nanostructured carbon materials. Nature Materials, 10, 581 (2011).
[2] D. L. Nika and A. A. Balandin, Phonons and thermal transport in graphene and graphene-based materials, Reports on Progress in Physics, 80, 36502 (2017).
[3] F. Kargar, Z. Barani, R. Salgado, B. Debnath, J.S. Lewis, E. Aytan, R.K. Lake, A.A. Balandin, Thermal percolation threshold and thermal properties of composites with high loading of graphene and boron nitride fillers, ACS Applied Materials and Interfaces, (2018) doi:10.1021/acsami.8b16616.

Since the discovery of the Quantum Spin Hall Effect, electronic and photonic topological insulators have made substantial progress, but phononic topological insulators in solids have received relatively little attention due to challenges in realizing topological states without spin-like degrees of freedom and with transverse phonon polarizations. Here we present a holey silicon-based phononic topological insulator design, in which simple geometric control enables topologically protected in-plane elastic wave propagation up to GHz ranges when the unit cell reaches submicron scales. By integrating a hexagonal lattice of six small holes with one large hole in the center and by creating a hexagonal lattice by themselves, the six-petal holey silicon, which has C₆ symmetry, induces zone folding to form a double Dirac cone. Based on the hole dimensions, breaking the discrete translational symmetry allows the six-petal holey silicon to achieve the topological phase transition, yielding two topologically distinct phononic crystals. Based on the unit cell periodicity, the transition readily shifts from low- to high-frequency ranges. Our numerical simulations confirm inverted band structures and show backscattering-immune elastic wave transmission up to 90 % at 14.83 GHz through defects including a cavity, a disorder, and sharp bends when the unit cell periodicity is 500√3 nm. The six-petal holey silicon design also offers robustness against geometric errors and potential fabrication issues such as over- or under-etching. The simulations of the six-petal holey silicon with the same periodicity show up to 90 % transmission of elastic waves at 13.8 and 15.37 GHz even when the holes are under-sized by 5 % or over-sized by 2.5 %, respectively, in which the shift of bandgap is led by the change of porosity. These findings provide a detailed understanding of the relationship between geometry and topological properties and pave the way for developing high-frequency phononic topological insulators and future phononic circuits.

Spectral emissivity control is critical for optical and thermal management in the ambient environment because solar irradiance and atmospheric transmissions occur at distinct wavelength regions. For instance, selective emitters with low emissivity in the solar spectrum but high emissivity in the mid-infrared can lead to significant radiative cooling. Ambient variations require not only spectral control but also a mechanism to adjust the emissivity. However, most selective emitters are fixed to specific wavelength ranges and lack dynamic control mechanisms. Here we show ultraviolet to mid-infrared emissivity control by mechanically reconfiguring graphene, in which stretching and releasing induce dynamic topographic changes. We fabricate crumpled graphene with pitches ranging from 40 nm to 10 µm using deformable substrates. Our measurements and computations show that 290-nm-pitch crumpled graphene offers ultraviolet emissivity control in 200-300 nm wavelengths whereas 10-µm-pitch crumpled graphene offers mid-infrared emissivity control in 7-19 µm wavelengths. Significant emissivity changes arise from interference induced by the periodic topography and selective transmissivity reductions. Dynamic stretching and releasing of 290-nm- and 10-µm-pitch crumpled graphene show reversible emissivity peak changes at 250 nm and at 9.9 µm wavelengths, respectively. This work demonstrates the unique potential of crumpled graphene as a reconfigurable optical and thermal management platform.

Plasmonic nanostructures generate heat via the photothermal effect when excited with a specific wavelength of light, where optically excited surface plasmons decay to produce hot electrons that subsequently couple to the lattice vibrations. Photothermal cancer therapy shows promise as an application using this effect, where local hyperthermia leads to cell death. However, noble metal nanoparticles traditionally used in plasmonic applications exhibit surface plasmon resonance in the lower-wavelength visible range, where human tissue is not transparent. As a result, recent research efforts have pushed new plasmonic nanostructures and materials into the near- and mid-infrared ranges by using anisotropic geometries. Gold nanorods are extensively used due to their wavelength tunability of the plasmon resonance and their ability to be modified and functionalized for specific binding, enhanced detection, and drug delivery. The thermal transport of this system at the cellular level is not heavily studied, therefore we experimentally measure the thermal transport in a system of cancer cells infiltrated with gold nanorods in vitro at various concentrations, to understand the minimum illumination intensities and durations required for cancer cell death. We report, for the first time, the interfacial thermal conductance between gold nanorods and the ovarian cancer cellular environment as measured by ultrafast pump-probe laser techniques. We also report the thermal conductivity and heat capacity of the cancer cells. By understanding the thermal properties of this system, more defined and tailored photothermal therapy regimens are made possible. This study also provides an experimental framework for measuring the thermal properties of other photothermal therapy agents in cellular environments in the future.

Aerospace applications in which high heat fluxes are reached necessitate the use of unique materials to withstand these harsh environments. The need for environmental barrier coatings (EBCs) are of particular importance in limiting the oxidation of aerospace components and the volatility of the SiO₂ scale commonly found in silicon-based ceramic coatings. Rare earth mono- and disilicates have been identified as promising EBCs due to their ease of application via various plasma spray processes. However, a robust examination of the insulating thermal properties of these systems has yet to be performed. To better understand the thermal processes and anisotropy associated with these disilicates, we examine the commonly used polymorph of yttrium disilicate, γ-Y₂Si₂O₇. Using a combination of time- and frequency-domain thermoreflectance, we compare the extracted thermal conductivity maps to associated electron backscatter diffraction micrographs. The thermal conductivity maps exhibit strong anisotropy in the monoclinic structure, in good agreement with other anisotropic features of the system. The results are significant in that they are the first experimental measurements of the anisotropic thermal conductivity in a thermal barrier coating, and should provide a basis for plasma-based applications in which the potential for texturing is strong.

Materials science is challenged with developing new materials in order to meet the demands of technological innovation. Consequently, this opens the door to novel or complex properties awaiting exploration. High entropy carbides (HECs) continue to demonstrate the viability of materials engineering using configurational entropy to aid in phase development. Using two compositions, Hf-Nb-Ta-Ti-Zr-C (HEC3) and Hf-Mo-Ta-W-Zr-C (HEC6), we explore the thermal transport properties of these systems as carbon stoichiometry is varied. Using time domain thermoreflectance (TDTR), we measure thermal conductivity of both the HEC3 and HEC6 thin film series and then relate trends to other observed characteristics of each system such as electrical conductivity, crystallinity, and modulus. Total thermal conductivity systematically varies with increasing deposition flow rate of methane, while the electrical contribution to the thermal conductivity decreases. Results are discussed in terms of various scattering mechanisms from different types of defects, emphasizing understanding of thermal properties from both a local and a global structural perspective. In this talk we focus on the experimental process of elimination using several metrology techniques in conjunction with TDTR to gain meaningful perspective on configurationally disordered, highly crystalline systems.

Wavelike thermal transport in solids, referred to as second sound, has until now been an exotic phenomenon limited to a handful of materials at low temperatures. This has restricted interest in its occurrence and in its potential applications. Through time-resolved optical measurements of thermal transport on 5-20 μm length scales in graphite, we have made direct observations of second sound at temperatures above 100 K. The results are in qualitative agreement with ab initio calculations that predict wavelike phonon hydrodynamics on ~ 1-μm length scale up to almost room temperature. The results suggest an important role of second sound in microscale transient heat transport in two-dimensional and layered materials in a wide temperature range.

As increasingly powerful microelectronic chips shrink in size and scale, inadequate waste heat dissipation ultimately results in poor computational performance or early device failure. Therefore, advances in thermal interface materials (TIMs) are necessary in combating detrimental heating issues by providing improved avenues for thermal transport. Many types of polymer-filler combinations for TIMs have been explored to maximize the composite thermal conductivity, while only leading to thermal conductivities of up to 2 W m^-1K^-1. One of the primary limitations to efficient thermal transport in TIMs lies in the boundary resistance generated by the point-contact of filler particles. Additionally, the thermally conductive inclusions are often rigid particles which can lower the elasticity of the composite at high fill factors. Increasing the effective contact area between filler materials could potentially result in much higher composite thermal conductivities [1,2]. Previous work done by Ralphs et al. has shown a substantial increase in thermal conductivity by up to 17 W m^-1K^-1with copper particles bridged by liquid metals in a PDMS matrix [3].
In this work, multi-phase fillers comprised of a solid metal core with a liquid metal shell are proposed as a promising solution to reducing point-contact boundary resistance. Liquid metals form a self-limiting oxide layer that encapsulates the liquid metal and can rupture under applied pressure, therefore allowing liquid metal coated particles to connect. Due to the tendency of liquid metals to alloy with and/or embrittle many metals, tungsten is selected as the core material for its relative inertness towards liquid metals. In addition, tungsten particles coated with liquid metals can also be mechanically processed to increase the effective contact area between adjacent particles. The novel combination of deformable liquid shells and highly thermally conductive solid particles can potentially lead to composite materials that facilitate more efficient heat transport and are still stretchable. This research seeks to demonstrate a reduction in thermal boundary resistance that improves TIMs through novel materials processing methods.
References:
[1] Mamunya et al. Eur. Polym. J. 2002. 8(9), 1887-1897.
[2] Seshadri et al. Adv. Mater. Interfaces. 2015. 27(17), 175601.
[3] Ralphs et al. ACS App. Mater Inter., 2018.10(2), 2083-2092.

Rechagrable Li-ion batteries (LIBs) are very promising candidates for electrochemical energy storage in electrical vechiles. Electrical conduction propeties in these systems are strongly affected by thermal transport properties during electrochemical cycling. Therefore, thermal management in these systems is very crucial for the control of electrical properties of these storage devices [1]. Si-based anode is a very attractive material because of potentially large achievable capacity of 3700 mAhg^-1 [2] that is ten times more than that for graphitic carbon, which is mainly used as an anode material in LIBs. However it is well known that Si electrodes suffer from volumetric change during the electrochemical cycling/recycling processes, which in turn leads to change in mechanical and electrical properties. But little research has been done on thermal conductivity variation in Si films during the lithiation. In this work we aim to study nanoscale thermal transport in this nanoscale-thick material using ex situ picosecond time-domain thermoreflectance (TDTR) approach [3]. RF magnetron sputtering was used to deposit a ~300 nm thick Si films on glass subatrate. A 50 nm thick Al was deposited on top of Si serving as an optical absorber and efficient heat transducer in TDTR experiments. The lithiation of films has been performed in the beaker cell with lithium hexafluorophosphate (LPF) in the solution of ethylene, diethyl carbonate and ethyl methyl carbonates (EC:DC:EMC = 1:1:1, v/v) using a constant current of 25 µA up to 0.05 V. Thermal transport measurements were done for non-lithiated and lithiated samples. The results show that for non-lithiated amorphous Si films the thermal conductivity value is ~ 1.4 W/m*K, which is very close to literature value [4]. After electrochemical lithation process, the thermal conductivity of lithiated amorphous Si was in the range between 1.3 to 2.2 W/m*K. This sizeable thermal transport fluctuation was likely due to inhomogeneous lateral Li ion distribution on the near-surface region. We also have done measurements on Young’s elastic modulus of these thin film materials using nanosecond laser pulse-induced surface acoustic waves. The results showed the decrease in Young’s modulus after lithiation as it is expected because of volumetric expansion of Si crystal.
Funding from MES RK state-targeted programs BR05236454, BR05236524 and grant AP05130446 is acknowledged.
References:
[1] J. Cho et al., Nature Communication, 5 (2014) 4035.
[2] C. J. Wen, R.A. Huggins, J. Solid State Chem. 37 (1981) 271.
[3] D.G. Cahill, Rev. Sci. Instrum. 75(12), 5119 (2004).
[4] S. Moon et al, Inter. J. Heat and Mass Transfer, 45 (2002) 2439.

Two fundamentally different avenues for controlling a materials thermal conductivity are phonon scattering and lattice softening. In the phonon scattering picture, the phonon dispersion relation and group velocities are assumed to be fixed and lattice defects reduce lattice thermal conductivity (κ_L) by introducing phonon scattering centers. Lattice softening recognizes that lattice defects alter the phonon dispersion relation and thus reduce κ_L by reducing phonon frequencies and group velocities. Here, I will present experimental data on several systems (Si, PbTe, and SnTe) which demonstrate that microstructural defects such as grain boundaries, dislocations, and vacancies can significantly softening a materials lattice, reducing the materials speed of sound and elastic moduli. By analyzing the data on elasticity and thermal conductivity through standard transport modeling, it is shown that lattice softening is a dominate mechanism for the reduction of κ_L in these systems. Additionally, it will be shown that lattice softening is theoretically expected to be more effective than phonon scattering effects in anharmonic materials and at high temperatures. This work demonstrates how lattice softening is emerging as an important mechanism for controlling a materials thermal conductivity, and provides new avenues to engineer a materials κ_L, beyond phonon scattering.

Gallium-based room temperature liquid metals have become a hot topic in the thermal management of traditional semiconductor packaging and stretchable electronics. However, the native gallium oxide shell on these liquids both facilitates many unique processing techniques as well as hinders others, making it a force that needs to be reckoned with. Some studies have been done on chemically and mechanically altering the oxide layer, but very few have focused on the thermal ramifications of the oxide and its rupture. In this work, we present a comprehensive set of experiments on parameters controlling fracturing of the oxide shell on micro and nanoscale liquid metal droplets and the resulting thermal conductivity of the droplet ensemble. Specifically, we fabricate liquid metal droplets with diameters ranging from hundreds of nanometers to ten micrometers and pack them into macroscopic films. We then compress the films while measuring thermal resistance, pressure, and electrical resistance in situthrough and beyond oxide rupture. This allows us to interrogate the mechanical role of the oxide layer and the thermal ramifications of the oxide shells when dealing with liquid metal droplets. Various sizes of liquid metal droplets are investigated as well as mixtures of liquid metal droplets and solid metal particles. The inclusion of solid and liquid metal particles together gives insight into the role of particle packing and how it relates to thermal resistance and oxide failure. The measured thermal properties and how they relate to the mechanics of the rupturing oxide will be explained. Additionally, this work will lead to insights on using liquid metal coated solid metal particles in a polymer composite to reduce the thermal boundary resistance between particles and greatly enhance the thermal conductivity of such composites.

Thermal energy storage devices (i.e. “thermal batteries) are utilized in scenarios where thermal energy is available at certain times but required for use at a later time. The amount of energy that can be stored within a thermal energy storage device depends on both the storage material and the mode of storage. Systems that incorporate thermochemical processes are often able to store significantly more energy than sensible and latent heat thermal energy storage systems.

This presentation focuses on the use of N-isopropylacrylamide (NIPAAm) for sorption thermal energy storage. NIPAAm is a thermoresponsive polymer that transitions from hydrophilic to hydrophobic upon crossing its critical temperature (typically 32 °C). In addition, NIPAAm has the ability to absorb water vapor (i.e. humidity) and expel liquid water. This creates huge energy savings potential during sorbent regeneration that is equivalent to the enthalpy of vaporization of water. The energy density of NIPAAm is also particularly attractive because it can be used in conjunction with hydrogels that can store up to 40 times the gel’s dehydrated mass in water.

To explore the potential of NIPAAm for cooling applications, we conduct system-level modeling of sorption systems utilizing this novel material. This system charges up by absorbing water from humid air that is passed through the device. When cooling is desired, the NIPAAm is heated above to 32 °C to expel liquid water that is then evaporated to cool the system. This sorption process can potentially exceed the energy density of traditional latent heat systems (e.g. cold thermal storage with ice) because the enthalpy of vaporization significantly exceeds the enthalpy of melting. The presentation on sorption system modeling with NIPAAm will highlight the exciting opportunities for this novel material in thermal energy storage applications.

The role of the computational material modeling and simulations is indispensable in the design and development of advanced materials with superior material properties. Here we present a coarse-grained molecular dynamics (CGMD) simulations-based investigation to understand a melting behavior of the mesoscopic electro-spun silica-nanofiber based insulator materials, and subsequently elucidate the silica nanofiber size-melting temperature relationship. A coarse-grain bead, which is equivalent to the spherical (SiO2)6 silica atomic structure, was used to construct the several mesoscopic silica nanofiber structures with sizes > 100 nm that were consequently simulated for several hundred nanoseconds. The temporal bead trajectory information was used to decipher the melting behavior of the silica nanofibers. The silica nanofiber size-melting temperature dependency evaluated through CGMD simulations could provide some valuable guidelines for the further optimization of the silica nanofiber manufacturing processes.

In the United States, nearly 68% of the primary energy produced each year is wasted as heat. A couple tangible examples of this wasted energy is the heat that radiates from laptops and air conditioning units that remove heat from air and release it into the environment. It would be efficient to convert this waste heat into a better source of energy such as current. Using the ferroelectric properties of BaTiO₃, this energy conversion can be done.

BaTiO₃ undergoes structural transitions when heat is applied at its curie temperature, approximately 120-130^ο C. During this structural transition, BaTiO₃ goes from paraelectric to ferroelectric. While in its ferroelectric state, BaTiO₃ behaves like a very good capacitor and during its paraelectric state, it behaves like a poor capacitor. Consequently, we can attach BaTiO₃ to a circuit with a reference capacitor (ordinary capacitor), and we can charge this circuit to equilibrium and remove all energy sources. As BaTiO₃ is heated and cooled, current flows from the reference capacitor to the activate BaTiO₃ capacitor. Experimentally, we have observed the current flows consistently as the heat oscillates in the curie temperature range.

Converting waste heat to current is an efficient energy conversion method.

In this work, we present an experimental study on magneto-thermal transport and spin-Seebeck effect behavior in ferromagnetic and semiconductor materials. The magneto-thermal transport measurements are carried out using in-plane self-heating three-omega method. The in-plane three-omega measurement requires a freestanding specimen. We address this challenge using micro-electro-mechanical systems (MEMS) fabrication methods. The measurements are carried out on Py/Au and Py/Si. We also demonstrate giant spin-Seebeck effect in Py/Si bilayer thin films. The mageto-thermal transport measurements on these thin films are essential for the design and development of energy efficient spintronics devices. We employ four point probe configuration for our MEMS device structure to probe mainly the second and third harmonic voltages as well as resistance with respect to changing temperature and applied magnetic field. The results can be related to thermal transport properties of the system using the three-omega method as mentioned above.

Disordered media are of special interest due to low thermal conductivity. Amorphous silicon (a-Si) has been widely used due to their low-cost potential. Due to the lack of long-range order, identifying thermal transport in a-Si has been challenging. For example, mean-free paths (MFPs) distribution of propagon, a propagating delocalized atomic vibrational state, and its contribution to the thermal conductivity have long been contentious. Here we report measurements of in-plane quasi-ballistic thermal transport from suspended a-Si thin film using transient grating spectroscopy. Our observations demonstrate that the phonons with grating period greater than 1 (mm) can contribute more than half to the thermal conductivity. Nearly temperature independent diffusivity further shows that anharmonic scattering may not be dominant over the temperature range that we studied: 30 (K) to 300 (K). Our non-contact measurement will provide useful insights into studying disordered materials that have been challenging with conventional thermal characterization methods.

Cubic boron arsenide (BAs) bulk crystal has been identified to have an ultrahigh thermal conductivity (~1300Wm^-1K^-1) both theoretically¹ and experimentally^2-4. On the other hand, two-dimensional (2D) stable monolayers of BAs have also been reported to have promising electronic, transport, optical and thermoelectric properties⁵. However, the thermal conductivity of BAs monolayer has not yet been investigated. Does thermal transport in BAs monolayers parallel that of cubic BAs bulk crystals? We present our first-principles study on the thermal conductivity of BAs monolayer.
The vibrational spectra of BAs monolayers have been calculated and are quite different from that of cubic BAs bulk crystals⁵. Two transversal acoustic and optical branches, which correspond to out-of-plane atomic vibrations in BAs monolayers, carry lower energy due to the fact that atoms can more easily vibrate perpendicular to the plane. The so-called “acoustic bunching” behavior in cubic BAs is also not seen in the vibrational spectra of BAs monolayer due to the presence of these out-of-plane branches. Nonetheless, the giant phononic band gap between the acoustic branches and two in-plane optical branches still exists in the vibrational spectra of BAs monolayers. At this point, qualitative analysis of thermal conductivity based on the vibration spectra is inconclusive. More rigorous computational calculations need to be performed to derive the lattice thermal conductivity of BAs monolayers.
For our computations, we employ density-functional perturbation theory to generate second-order (harmonic) and third-order (anharmonic) interatomic force constants (IFC) for BAs monolayer using the VASP package. The harmonic IFC allows us to derive the vibrational properties, while the anharmonic IFC allows us to determine the three-phonon scattering rates using Fermi’s golden rule. With the only inputs of harmonic and anharmonic IFC, we can derive the lattice thermal conductivity by solving the exact phonon Boltzmann Transport Equation using the ShengBTE package⁶.
Reference:
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2. F. Tian, B. Song, X. Chen, N. K. Ravichandran, Y. C. Lv, K. Chen, S. Sullivan, J. Kim, Y. Y. Zhou, T. H. Liu, M. Goni, Z. W. Ding, J. Y. Sun, G. A. G. U. Gamage, H. R. Sun, H. Ziyaee, S. Y. Huyan, L. Z. Deng, J. S. Zhou, A. J. Schmidt, S. Chen, C. W. Chu, P. S. E. Y. Huang, D. Broido, L. Shi, G. Chen and Z. F. Ren, Science, 2018, 361, 582.
3. J. S. Kang, M. Li, H. A. Wu, H. Nguyen and Y. J. Hu, Science, 2018, 361, 575-578.
4. S. Li, Q. Y. Zheng, Y. C. Lv, X. Y. Liu, X. Q. Wang, P. S. E. Y. Huang, D. G. Cahill and B. Lv, Science, 2018, 361, 579-581.
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In aerospace applications operating at very high temperatures (> 3000 K), such as hypersonic flight or rocket propulsion systems, there is a critical need for the development of materials which can survive such extreme temperatures. To meet this need, ultra-high temperature ceramics (UHTCs) have proven to be at the forefront of research. While early development of UHTCs were primarily focused on SiC and Si₃N₄, currently there is a strong interest in transition metal diborides such as hafnium diboride (HfB₂) and zirconium diboride (ZrB₂) as well as carbides such as hafnium carbide (HfC) and tantalum carbide (TaC). Looking beyond binary carbides and diborides, materials synthesis of high-entropy ceramics consisting of five or more elements has enabled a new research direction to explore the engineering of thermophysical properties to enable sustainable high-temperature application. One of the most critical properties to understand in these systems is thermal conductivity. While bulk thermal conductivity measurements provide a metric for determining how heat flows on average in the material, these techniques disregard any insight into microstructure on thermal transport. Because failure can occur due to local weak points, it is therefore necessary to probe local thermal properties to understand the microstructural impacts on thermal transport.

To this end, here we use time-domain thermoreflectance (TDTR) to conduct thermal mapping over a large area to resolve localized thermal conductivity as a function of real space. Paired with Scanning Electron Microscope (SEM) and Electron Backscatter Diffraction (EBSD) images, we relate local properties to crystal orientation and microstructure. We measure the thermal conductivity of a high entropy diboride (HfZrTaNbTi)B₁₀ and high entropy carbide (HfNbTaTiZr)C₅. Using TDTR, we map the thermal conductivity of these bulk samples, which have ~30 micron grains. Comparison of the thermal conductivity map to SEM and EBSD images reveals the role of anisotropy and grain boundary scattering of electrons and phonons on reducing the overall thermal conductivities of these samples.

Theoretical studies have shown that solar thermophotovoltaic (STPV) systems have the potential to produce efficiencies up to 85%, but current technology has only reported actual efficiencies around 6.8%. Studies have clearly shown that the major drawbacks in the components of a STPV system are the solar absorber and emitter. Current solar absorbers have shown to have high thermal emission causing heat loss and emitters display a lack in thermal emission above the bandgap of TPV cells. It is desired to have a solar absorber with unit absorptance in the solar spectrum, while having zero emittance in the longer wavelengths. In addition to this, emitters need to have unity emittance only within a narrow band that matches the high quantum efficiency of a specific TPV cell to minimize non-useful photons. Our experimental study will mainly address the issue of high thermal emission of solar absorbers by applying the highly-efficient selective metafilm coating recently developed in our lab. We propose to use the metafilm which has demonstrated high temperature thermal stability, as a solar absorber to investi