Tuning Thermal Conductivity of Hybrid Perovskites through Halide Alloying.

Tuning the thermal transport properties of hybrid halide perovskites is critical for their applications in optoelectronics, thermoelectrics, and photovoltaics. Here, an effective strategy is demonstrated to modulate the thermal transport property of hybrid perovskites by halide alloying. A highly tunable thermal conductivity of mixed-halide hybrid perovskites is achieved due to halide-alloying and structural distortion. The experimental measurements show that the room temperature thermal conductivity of MAPb(BrxI1- x)3 (x = 0─1) can be largely modulated from 0.27 ± 0.07 W m-1 K-1 (x = 0.5) to 0.47 ± 0.09 W m-1 K-1 (x = 1). Molecular dynamics simulations further demonstrate that the thermal conductivity reduction of hybrid halide perovskites results from the suppression of the mean free paths of the low-frequency acoustic and optical phonons. It is found that halide alloying and the induced structural distortion can largely increase the scatterings of optical and acoustic phonons, respectively. The confined diffusion of MA+ cations in the octahedra cage is found to act as an additional thermal transport channel in hybrid perovskites and can contribute around 10-20% of the total thermal conductivity. The findings provide a strategy for tailoring the thermal transport in hybrid halide perovskites, which may largely benefit their related applications.

Direct observation of tunable thermal conductance at solid/porous crystalline solid interfaces induced by water adsorbates.

Improving interfacial thermal transport is crucial for heat dissipation in devices with interfaces, such as electronics, buildings, and solar panels. Here, we design a strategy by utilizing the water adsorption-desorption process in porous metal-organic frameworks (MOFs) to tune the interfacial heat transfer, which could benefit their potential in cooling or heat dissipation applications. We observe a changeable thermal conductance across the solid/porous MOF interfaces owing to the dense water channel formed by the adsorbed water molecules in MOFs. Our experimental and/or modeling results show that the interfacial thermal conductance of Au/Cu3(BTC)2, Au/Zr6O4(OH)4(BDC)6 and Au/MOF-505 heterointerfaces is increased up to 7.1, 1.7 and 3.1 folds by this strategy, respectively, where Cu3(BTC)2 is referred to as HKUST-1 and Zr6O4(OH)4(BDC)6 is referred to as UiO-66. Our molecular dynamics simulations further show that the surface tension of Au layer will cause the adsorbed water molecules in MOFs to gather at the interfacial region. The dense water channel formed at the interfacial region can activate the high-frequency lattice vibrations and act as an additional thermal pathway, and then enhance heat transfer across the interfaces significantly. Our findings revealed the underlying mechanisms for tailoring thermal transport at the solid/porous MOF heterointerfaces by water adsorbates, which could motivate and benefit the new cooling system design based on MOFs.

Effects of Thermal Boundary Resistance on Thermal Management of Gallium-Nitride-Based Semiconductor Devices: A Review.

Wide-bandgap gallium nitride (GaN)-based semiconductors offer significant advantages over traditional Si-based semiconductors in terms of high-power and high-frequency operations. As it has superior properties, such as high operating temperatures, high-frequency operation, high breakdown electric field, and enhanced radiation resistance, GaN is applied in various fields, such as power electronic devices, renewable energy systems, light-emitting diodes, and radio frequency (RF) electronic devices. For example, GaN-based high-electron-mobility transistors (HEMTs) are used widely in various applications, such as 5G cellular networks, satellite communication, and radar systems. When a current flows through the transistor channels during operation, the self-heating effect (SHE) deriving from joule heat generation causes a significant increase in the temperature. Increases in the channel temperature reduce the carrier mobility and cause a shift in the threshold voltage, resulting in significant performance degradation. Moreover, temperature increases cause substantial lifetime reductions. Accordingly, GaN-based HEMTs are operated at a low power, although they have demonstrated high RF output power potential. The SHE is expected to be even more important in future advanced technology designs, such as gate-all-around field-effect transistor (GAAFET) and three-dimensional (3D) IC architectures. Materials with high thermal conductivities, such as silicon carbide (SiC) and diamond, are good candidates as substrates for heat dissipation in GaN-based semiconductors. However, the thermal boundary resistance (TBR) of the GaN/substrate interface is a bottleneck for heat dissipation. This bottleneck should be reduced optimally to enable full employment of the high thermal conductivity of the substrates. Here, we comprehensively review the experimental and simulation studies that report TBRs in GaN-on-SiC and GaN-on-diamond devices. The effects of the growth methods, growth conditions, integration methods, and interlayer structures on the TBR are summarized. This study provides guidelines for decreasing the TBR for thermal management in the design and implementation of GaN-based semiconductor devices.

The interfacial thermal conductance spectrum in nonequilibrium molecular dynamics simulations considering anharmonicity, asymmetry and quantum effects.

Interfacial thermal transport is critical for many thermal-related applications such as heat dissipation in electronics. While the total interfacial thermal conductance (ITC) can be easily measured or calculated, the ITC spectral mapping has been investigated only recently and is not fully understood. By combining nonequilibrium molecular dynamics simulations and atomistic Green's function method, we systematically investigate the ITC spectrum across an ideal interface, i.e., the argon/heavy argon interface. Our results show that the ITC increases gradually with temperature as more phonons and anharmonic scattering channels are activated, e.g., the vibrations with frequencies larger than 1 THz can contribute 5% (15%) to the total ITC at 2 K (40 K) through anharmonic phonon scattering channels. We further find that the ITC spectrum from the left interfacial Hamiltonian is quite different from that of the right interfacial Hamiltonian, which stems from the asymmetry of anharmonic phonon scatterings caused by the dissimilar vibrational properties of the two interfacial contacts. While all the phonons are involved in the anharmonic scatterings for the heavy argon interfacial Hamiltonian, the phonons involved in the anharmonic phonon scatterings from the argon interfacial Hamiltonians are mainly the vibrations with frequency smaller than 1 THz (i.e., the cut-off frequency of heavy argon). Finally, we found that the quantum effect is important for the ITC spectrum at low temperatures, e.g., below 30 K in our systems. Our findings are also applicable to other interfaces, e.g., Si/Ge interfaces. Our study here systematically investigates the influence of anharmonicity, asymmetry, and quantum effects on the ITC spectrum, which is critical for designing and optimizing interfaces for better performance.

Highly Thermo-Conductive Three-Dimensional Graphene Aqueous Medium.

Highly thermo-conductive aqueous medium is a crucial premise to demonstrate high-performance thermal-related applications. Graphene has the diamond comparable thermal conductivity, while the intrinsic two-dimensional reality will result in strong anisotropic thermal conductivity and wrinkles or even crumples that significantly sacrifices its inherent properties in practical applications. One strategy to overcome this is to use three-dimensional (3D) architecture of graphene. Herein, 3D graphene structure with covalent-bonding nanofins (3D-GS-CBF) is proposed, which is then used as the filler to demonstrate effective aqueous medium. The thermal conductivity and thermal conductivity enhancement efficiency of 3D-GS-CBF (0.26 vol%) aqueous medium can be as high as 2.61 W m-1 K-1 and 1300%, respectively, around six times larger than highest value of the existed aqueous mediums. Meanwhile, 3D-GS-CBF can be stable in the solution even after 6 months, addressing the instability issues of conventional graphene networks. A multiscale modeling including non-equilibrium molecular dynamics simulations and heat conduction model is applied to interpret experimental results. 3D-GS-CBF aqueous medium can largely improve the solar vapor evaporation rate (by 1.5 times) that are even comparable to the interfacial heating system; meanwhile, its cooling performance is also superior to commercial coolant in thermal management applications.

Author Correction: Thermal transport crossover from crystalline to partial-crystalline partial-liquid state.

The original version of this Article incorrectly omitted an affiliation of Sebastian Volz: 'LIMMS/CNRS-IIS(UMI2820) Institute of Industrial Science, University of Tokyo 4-6-1 Komaba, Meguro-ku Tokyo 153-8505 JAPAN'. This has now been corrected in both the PDF and HTML versions of the Article.

Thermal transport crossover from crystalline to partial-crystalline partial-liquid state.

Phase-change materials (crystalline at low temperatures and partial-crystalline partial-liquid state at high temperatures) are widely used as thermoelectric converters and battery electrodes. Here, we report the underlying mechanisms driving the thermal transport of the liquid component, and the thermal conductivity contributions from phonons, vibrations with extremely short mean free path, liquid and lattice-liquid interactions in phase-changed Li2S. In the crystalline state (T ≤ 1000 K), the temperature dependent thermal conductivity manifests two different behaviors, i.e., a typical trend of 1/T below 800 K and an even faster decrease between 800 and 1000 K. For the partial-crystalline partial-liquid Li2S when T ≥ 1100 K, the contributions of liquid and lattice-liquid interactions increase significantly due to the fluidization of Li ions, and the vibrations with extremely short mean free path, presumably assimilated to diffusons, can contribute up to 46% of the total thermal conductivity at T = 1300 K.

Two-Channel Thermal Transport in Ordered-Disordered Superionic Ag2Te and Its Traditionally Contradictory Enhancement by Nanotwin Boundary.

A recent experiment [ J. Mater. Chem. A 2015 , 3 , 10303 ] has proved that superionic Ag2Te can achieve a figure of merit as high as 1.39 due to its extremely low thermal conductivity. However, the traditional lattice vibration concept, i.e., phonons regarded as heat carriers, fails to explain the governing mechanism in such structures where anions vibrate around their equilibrium positions while cations flow like a liquid. As a result, the underlying physics for thermal transport properties in superionic Ag2Te is still a mystery. In this study, two-channel heat transport in such ordered-disordered systems (i.e., lattice vibrations and liquid-like mobile ions coexist) is quantitatively characterized on the basis of the heat flux linear response theory. Our results show that the convective thermal conductivity is dominant in the system, which results from the free movement of Ag ions. As a consequence, the total thermal conductivity increases abnormally with temperature due to the strengthened cations' mobilities at elevated temperatures. Meanwhile, the effect of experimentally observed nanotwin boundaries [ Acta Mater. 2017 , 128 , 43 ], which facilitate electrical transport in crystals, on heat carriers are also investigated. In contradiction to the classical heat transport theory, in which heat carriers are hindered by boundaries, the nanotwin boundary in superionic Ag2Te unexpectedly improves thermal transport due to the enhanced movement of Ag ions around the grain boundary. This exhaustive explanation of thermal transport properties in superionic Ag2Te will support the future design of superionic conductors based on thermoelectrics and more broad energy systems composed of ordered-disordered materials.

Methodology Perspective of Computing Thermal Transport in Low-Dimensional Materials and Nanostructures: The Old and the New.

Demands for engineering thermal transport properties are ever increasing for a wide range of modern micro- and nanodevices and materials-based energy technologies. In particular, there is a severe situation due to the rapid progress in the synthesis and processing of materials and devices with structural characteristic length on the nanometer scales, which are comparable or even smaller than the intrinsic length scales (such as mean free path and wavelength) of basic energy carriers (such as phonons, electrons, and photons). Although advanced approaches for controlling the electronic and photonic transport have been proposed in the past decades, progress on controlling lattice vibrations (i.e., the phonons) is still far behind. Gaps between the fundamental understandings of the behavior of the basic energy carriers at small scales and the technological demands still remain, particularly from a computer modeling point of view. Herewith, we give a perspective of the computational approaches for predicting the thermal transport properties of low-dimensional materials and nanostructures, which are mainly sorted into three categories: empirical molecular dynamics, anharmonic lattice dynamics based Boltzmann transport equation, and Landauer theory. The advantage and disadvantage of each method are discussed and some possible solutions are suggested. The discussion is focused on fully and accurately characterizing the mode-level phonon behavior, possible all-order phonon scattering process, and incorporation of realistic nanostructures. Moreover, emerging challenges of phonon coupling effects, such as electron-phonon, phonon-photon, and phonon-magnon coupling, are also discussed. We expect that this perspective will stimulate future research in computer modeling of micro-/nanoscale heat transfer beyond traditional phonons.

Decouple electronic and phononic transport in nanotwinned structures: a new strategy for enhancing the figure-of-merit of thermoelectrics.

Thermoelectric (TE) materials manifest themselves to enable direct conversion of temperature differences to electric power and vice versa. Though remarkable advances have been achieved in the past decades for various TE systems, the energy conversion efficiency of TE devices, which is characterized by a dimensionless figure-of-merit (ZT = S2σT/(κel + κph)), generally remains a poor factor that severely limits TE devices' competitiveness and range of employment. The bottleneck for substantially boosting the ZT coefficient lies in the strong interdependence of the physical parameters involved in electronic (S and σ, and κel) and phononic (κph) transport. Herein, we propose a new strategy of incorporating nanotwinned structures to decouple electronic and phononic transport. Combining the new concept of nanotwinned structures with the previously widely used nanocrystalline approach, the power factor of the nanotwin-nanocrystalline Si heterostructures is enhanced by 120% compared to that of bulk crystalline Si, while the lattice thermal conductivity is reduced to a level well below the amorphous limit, yielding a theoretical limit of 0.52 and 0.9 for ZT coefficient at room temperature and 1100 K, respectively. This value is almost two orders of magnitude larger than that for bulk Si and twice that for polycrystalline Si. Even for the experimentally obtained nanotwin-nanocrystalline heterostructures (e.g. grain size of 5 nm), the ZT coefficient can be as high as 0.26 at room temperature and 0.7 at 1100 K, which is the highest ZT value among all Si-based bulk nanostructures found thus far. Such substantial improvement stems from two aspects: (1) the improvement in the power factor is caused due to an increase in the Seebeck coefficient (degeneracy of the band valley) and the enhancement of electrical conductivity (the reduction of the effective band mass) and (2) the significant reduction of the lattice thermal conductivity is mainly caused due to the extremely strong phonon-grain boundary and phonon-twin boundary scattering. Our results suggest that nanotwinned structures are excellent building blocks for enhancing TE performance in diamond-like semiconductors, and our study provides a new strategy for the innovative development of other TE materials.

Nonmonotonic Diameter Dependence of Thermal Conductivity of Extremely Thin Si Nanowires: Competition between Hydrodynamic Phonon Flow and Boundary Scattering.

By carefully and systematically performing Green-Kubo equilibrium molecular dynamics simulations, we report that the thermal conductivity (κ) of Si nanowires (NWs) does not diverge but converges and increases steeply when NW diameter (D) becomes extremely small (dκ/dD < 0), a long debate of one-dimensional heat conduction in history. The κ of the thinnest possible Si NWs reaches a superhigh level that is as large as more than 1 order of magnitude higher than its bulk counterpart. The abnormality is explained in terms of the dominant normal (N) process (energy and momentum conservation) of low frequency acoustic phonons that induces hydrodynamic phonon flow in the Si NWs without being scattered. With D increasing, the downward shift of optical phonons triggers strong Umklapp (U) scattering with acoustic phonons and attenuates the N process, leading to the regime of phonon boundary scattering (dκ/dD < 0). The two competing mechanisms result in nonmonotonic diameter dependence of κ with minima at critical diameter of 2-3 nm. Our results unambiguously demonstrate the converged κ and the clear trend of κ ∼ D for extremely thin Si NWs by fully elucidating the competition between the hydrodynamic phonon flow and phonon boundary scattering.

Record Low Thermal Conductivity of Polycrystalline Si Nanowire: Breaking the Casimir Limit by Severe Suppression of Propagons.

Thermoelectrics offer an attractive pathway for addressing an important niche in the globally growing landscape of energy demand. Nanoengineering existing low-dimensional thermoelectric materials pertaining to realizing fundamentally low thermal conductivity has emerged as an efficient route to achieve high energy conversion performance for advanced thermoelectrics. In this paper, by performing nonequilibrium and Green-Kubo equilibrium molecular dynamics simulations we report that the thermal conductivity of Si nanowires (NWs) in polycrystalline form can reach a record low value substantially below the Casimir limit, a theory of diffusive boundary limit that regards the direction-averaged mean free path is limited by the characteristic size of the nanostructures. The astonishingly low thermal conductivity of polycrystalline Si NW is 269 and 77 times lower with respect to that of bulk Si and pristine Si NW, respectively, and is even only about one-third of the value of the purely amorphous Si NW at room temperature. By examining the mode level phonon behaviors including phonon group velocities, lifetime, and so forth, we identify the mechanism of breaking the Casimir limit as the strong localization of the middle and high frequency phonon modes, which leads to a prominent decrease of effective mean free path of the heat carriers including both propagons and diffusons. The contribution of the propagons to the overall thermal transport is further quantitatively characterized and is found to be dramatically suppressed in polycrystalline Si NW form as compared with bulk Si, perfect Si NW, and pure amorphous Si NW. Consequently, the diffusons, which transport the heat through overlap with other vibrations, carry the majority of the heat in polycrystalline Si NWs. We also proposed approach of introducing "disorder" in the polycrystalline Si NWs that could eradicate the contribution of propagons to achieve an even lower thermal conductivity than that ever thought possible. Our investigation provides a deep insight into the thermal transport in polycrystalline NWs and offers a promising strategy to construct a new kind of semiconducting thermoelectric NW with high figure of merit.

Strong Surface Orientation Dependent Thermal Transport in Si Nanowires.

Thermoelectrics, which convert waste heat to electricity, offer an attractive pathway for addressing an important niche in the globally growing landscape of energy demand. Research to date has focused on reducing the thermal conductivity relative to the bulk. Si nanowires (NWs) have received exceptional attention due to their low-dimensionality, abundance of availability, and high carrier mobility. From thermal transport point of view, the thermal conductivity of Si NWs strongly depends on the detailed surface structure, such as roughness and surface orientation. Here, direct molecular dynamics simulations and theoretical models are used to investigate the thermal transport in Si NWs with diverse surface orientations. Our results show that the thermal conductivity of Si NWs with different surface orientation can differ by as large as 2.7~4.2 times, which suggests a new route to boost the thermoelectric performance. Using the full spectrum theory, we find that the surface orientation, which alters the distribution of atoms on the surface and determines the degree of phonon coupling between the core and the surface, is the dominant mechanism. Furthermore, using spectral thermal conductivity, the remarkable difference in the thermal conductivity for different surface orientation is found to only stem from the phonons in the medium frequency range, with minor contribution from low and high frequency phonons.

An excellent candidate for largely reducing interfacial thermal resistance: a nano-confined mass graded interface.

Pursuing extremely low interfacial thermal resistance has long been the task of many researchers in the area of nano-scale heat transfer, in particular pertaining to improve heat dissipation performance in electronic cooling. While it is well known and documented that confining a macroscopic third layer between two dissimilar materials usually increases the overall interfacial thermal resistance, no research has realized the fundamental decrease in resistance so far. By performing nonequilibrium molecular dynamics simulations, we report that the overall interfacial thermal resistance can be reduced by 6 fold by confining mass graded materials with thickness of the order of nanometers. As comparison we also studied the thermal transport across the perfectly abrupt interface and the widely used alloyed (rough) interface, which shows an opposing and significantly large increase in the overall thermal resistance. With the help of frequency dependent interfacial thermal conductance and wave packet dynamics simulation, different mechanisms governing the heat transfer across these three types of interfaces are identified. It is found that for the rough interface there are two different regimes of interfacial heat transfer, which originates from the competition between phonon scattering and the thickness of the interface. The mechanism of dramatically improved interfacial heat transfer across the nano-confined mass graded interface resides in the minor phonon reflection when the phonons first reach the mass graded area and the rare occurrence of phonon scattering in the subsequent interior region. The phonons are found to be gradually truncated by the geometric interfaces and can travel through the mass graded layer with a high transmission coefficient, benefited from the small mass mismatch between two neighboring layers in the interfacial region. Our findings provide deep insight into the phonon transport across nano-confined mass graded layers and also offer significant guidance for designing advanced thermal interface materials.