Unwrapping a full temporal cycle in time domain thermoreflectance for enhanced measurement sensitivity in thermally insulating materials.

Time delayed pump-probe measurement techniques, such as Time Domain Thermoreflectance (TDTR), have opened up a wealth of opportunities for metrology at ultra-fast timescales and nanometer length scales. For nanoscale thermal transport measurements, typical thermal lifetimes used to measure thermal conductivity and thermal boundary conductance span from sub-picosecond to ∼6 nanoseconds. In this work, we demonstrate a simple rearrangement and validation of a configuration that allows access to the entire 12.5 ns time delay available in the standard pulse train. By reconfiguring a traditional TDTR system so that the pump and probe arrive concurrently when the delay stage reaches its midpoint, followed by unwrapping the temporal scan, we obtain a dataset that is bounded only by the oscillator repetition rate. Sensitivity analysis along with conducted measurements shows that great increases in measurement sensitivity are available with this approach, particularly for thin films with low thermal conductivities.

Theoretical Paradigm for Thermal Rectification via Phonon Filtering and Spectral Confinement.

Significant thermal rectification has the potential to revolutionize approaches to controlled heat flow and enable breakthrough technologies such as phononic computing. We demonstrate a framework based on phonon population confinement and filtering that has potential to reach rectifications that are an order of magnitude larger than previous literature. With the use of a straightforward modification of the phonon gas model, we illustrate theoretical thermal rectification in a thin film of diamond (1-10 nm) graded to dimensions >1 µm of between 25% and 250%. Utilizing this mechanism for thermal rectification sets the stage for significant development in thermal devices.

High resolution steady-state measurements of thermal contact resistance across thermal interface material junctions.

Thermal interface materials (TIMs) are meant to reduce the interfacial thermal resistance (RT) across bare metal contacts in commercial electronics packaging systems. However, there is little scientific consensus governing material design for optimized thermal performance. This is principally due to the inability to separate the effects of the intrinsic material thermal properties from the magnitude of heat flow crossing the TIM-substrate junction (RC). To date, efforts to isolate these effects using standard thermal interface material characterization techniques have not been successful. In this work, we develop an infrared thermography-based steady-state heat meter bar apparatus with a novel in situ thickness measurement system having 0.5 nm sensitivity. These in situ thickness measurements allow us to simultaneously determine RT and RC independently across current state-of-the-art TIMs with ±5% uncertainty. In this work, thermal pastes with bond line thicknesses ranging between 5 and 50 µm are used to illustrate the capability of the apparatus to measure extremely thin materials that are expected to achieve relatively low values of RT. Results suggest that the contribution of the thermal contact resistance to the total thermal resistance can range from 5% to 80% for these materials. This finding highlights the need for appropriate metrology and independent measurements of RC and RT to better optimize thermal interface materials for a number of important electronics applications.

Molecular Tuning of the Vibrational Thermal Transport Mechanisms in Fullerene Derivative Solutions.

Control over the thermal conductance from excited molecules into an external environment is essential for the development of customized photothermal therapies and chemical processes. This control could be achieved through molecule tuning of the chemical moieties in fullerene derivatives. For example, the thermal transport properties in the fullerene derivatives indene-C60 monoadduct (ICMA), indene-C60 bisadduct (ICBA), [6,6]-phenyl C61 butyric acid methyl ester (PCBM), [6,6]-phenyl C61 butyric acid butyl ester (PCBB), and [6,6]-phenyl C61 butyric acid octyl ester (PCBO) could be tuned by choosing a functional group such that its intrinsic vibrational density of states bridge that of the parent molecule and a liquid. However, this effect has never been experimentally realized for molecular interfaces in liquid suspensions. Using the pump-probe technique time domain thermotransmittance, we measure the vibrational relaxation times of photoexcited fullerene derivatives in solutions and calculate an effective thermal boundary conductance from the opto-thermally excited molecule into the liquid. We relate the thermal boundary conductance to the vibrational modes of the functional groups using density of states calculations from molecular dynamics. Our findings indicate that the attachment of an ester group to a C60 molecule, such as in PCBM, PCBB, and PCBO, provides low-frequency modes which facilitate thermal coupling with the liquid. This offers a channel for heat flow in addition to direct coupling between the buckyball and the liquid. In contrast, the attachment of indene rings to C60 does not supply the same low-frequency modes and, thus, does not generate the same enhancement in thermal boundary conductance. Understanding how chemical functionalization of C60 affects the vibrational thermal transport in molecule/liquid systems allows the thermal boundary conductance to be manipulated and adapted for medical and chemical applications.

Effect of graphene layer thickness and mechanical compliance on interfacial heat flow and thermal conduction in solid-liquid phase change materials.

Solid-liquid phase change materials (PCMs) are attractive candidates for thermal energy storage and electronics cooling applications but have limited applicability in state-of-the-art technologies due to their low intrinsic thermal conductivities. Recent efforts to incorporate graphene and multilayer graphene into PCMs have led to the development of thermal energy storage materials with remarkable values of bulk thermal conductivity. However, the full potential of graphene as a filler material for the thermal enhancement of PCMs remains unrealized, largely due to an incomplete understanding of the physical mechanisms that govern thermal transport within graphene-based nanocomposites. In this work, we show that the number of graphene layers (n) within an individual graphene nanoparticle has a significant effect on the bulk thermal conductivity of an organic PCM. Results indicate that the bulk thermal conductivity of PCMs can be tuned by over an order of magnitude simply by adjusting the number of graphene layers (n) from n = 3 to 44. Using scanning electron microscopy in tandem with nanoscale analytical techniques, the physical mechanisms that govern heat flow within a graphene nanocomposite PCM are found to be nearly independent of the intrinsic thermal conductivity of the graphene nanoparticle itself and are instead found to be dependent on the mechanical compliance of the graphene nanoparticles. These findings are critical for the design and development of PCMs that are capable of cooling next-generation electronics and storing heat effectively in medium-to-large-scale energy systems, including solar-thermal power plants and building heating and cooling systems.