Thomas L. Bougher

High thermal conductivity of chain-oriented amorphous polythiophene

Polymers are usually considered thermal insulators, because the amorphous arrangement of the molecular chains reduces the mean free path of heat-conducting phonons. The most common method to increase thermal conductivity is to draw polymeric fibres, which increases chain alignment and crystallinity, but creates a material that currently has limited thermal applications. Here we show that pure polythiophene nanofibres can have a thermal conductivity up to ∼ 4.4 W m(-1) K(-1) (more than 20 times higher than the bulk polymer value) while remaining amorphous. This enhancement results from significant molecular chain orientation along the fibre axis that is obtained during electropolymerization using nanoscale templates. Thermal conductivity data suggest that, unlike in drawn crystalline fibres, in our fibres the dominant phonon-scattering process at room temperature is still related to structural disorder. Using vertically aligned arrays of nanofibres, we demonstrate effective heat transfer at critical contacts in electronic devices operating under high-power conditions at 200 °C over numerous cycles.

A carbon nanotube optical rectenna

An optical rectenna--a device that directly converts free-propagating electromagnetic waves at optical frequencies to direct current--was first proposed over 40 years ago, yet this concept has not been demonstrated experimentally due to fabrication challenges at the nanoscale. Realizing an optical rectenna requires that an antenna be coupled to a diode that operates on the order of 1 PHz (switching speed on the order of 1 fs). Diodes operating at these frequencies are feasible if their capacitance is on the order of a few attofarads, but they remain extremely difficult to fabricate and to reliably couple to a nanoscale antenna. Here we demonstrate an optical rectenna by engineering metal-insulator-metal tunnel diodes, with a junction capacitance of ∼2 aF, at the tip of vertically aligned multiwalled carbon nanotubes (∼10 nm in diameter), which act as the antenna. Upon irradiation with visible and infrared light, we measure a d.c. open-circuit voltage and a short-circuit current that appear to be due to a rectification process (we account for a very small but quantifiable contribution from thermal effects). In contrast to recent reports of photodetection based on hot electron decay in a plasmonic nanoscale antenna, a coherent optical antenna field appears to be rectified directly in our devices, consistent with rectenna theory. Finally, power rectification is observed under simulated solar illumination, and there is no detectable change in diode performance after numerous current-voltage scans between 5 and 77 °C, indicating a potential for robust operation.

Carbon nanotube thermal interfaces enhanced with sprayed on nanoscale polymer coatings

Vertical carbon nanotube (CNT) forests bonded at room temperature with sprayed on nanoscale polymer coatings are found by measurement to produce thermal resistances that are on a par with those of conventional metallic solders. These results are achieved by reducing the high contact resistance at CNT tips, which has hindered the development of high performance thermal interface materials based on CNTs. A spray coating process is developed for depositing nanoscale coatings of polystyrene and poly-3-hexylthiophene onto CNT forests, as a bonding agent that mitigates thermal resistance by enhancing the area available for heat transfer at CNT contacts. Resistances as low as 4.9 ± 0.3 mm(2) K W(-1) are achieved for the entire polymer coated CNT interface structure. The suitability of the spray coating process for large-scale implementation and the role of polymer and CNT forest thickness in determining the thermal resistance are also examined.

Thermal Boundary Resistance in GaN Films Measured by Time Domain Thermoreflectance with Robust Monte Carlo Uncertainty Estimation

ABSTRACT In this work, we investigate the thermal boundary resistance and thermal conductivity of GaN layers grown on Si with 100 nm AlN transition layers using time domain thermoreflectance (TDTR). The GaN layers ranged from 0.31 to 1.27 μm. Due to the challenges in determining the thermal boundary resistance of the buried interfaces found in this architecture, a new data reduction scheme for TDTR that utilizes a Monte Carlo fitting method is introduced and found to dramatically reduce the uncertainty in certain model parameters. The results show that the GaN thermal conductivity does not change significantly with layer thickness, whereas the resistance of the AlN layer decreases slightly with GaN thickness.

Postgrowth Microwave Treatment to Align Carbon Nanotubes

We show that a commercial microwave oven can be used after growth to increase alignment of carbon nanotubes (CNTs) and reduce their resistance as thermal and electrical interface materials. Forests of multiwall CNTs were grown directly on both sides of aluminum foils by thermal chemical vapor deposition (CVD) and subsequently exposed to a microwave treatment in air. Scanning electron micrographs revealed enhanced vertical alignment of CNTs after postgrowth microwave treatment. The microwave treatment creates an electric field near the CNT growth substrate that aligns the CNTs orthogonally to the growth substrate. Microwaved CNT forests produced increased mechanical stiffness by approximately 58%, and reduced thermal and electrical contact resistances by 44% and 41%, respectively, compared to as-grown forests. These performance changes are attributed to an increase in the real contact area established at the CNT distal ends because of the enhanced forest alignment. This conclusion is consistent with several prior observations in the literature. This work demonstrates a facile method to enhance the alignment of CNTs grown by thermal CVD without the use of in situ plasma or electric field application. [DOI: 10.1115/1.4023162]

Thermal conductivity enhancement of laser induced graphene foam upon P3HT infiltration

Significant research has been dedicated to the exploration of high thermal conductivity polymer composite materials with conductive filler particles for use in heat transfer applications. However, poor particle dispersibility and interfacial phonon scattering have limited the effective composite thermal conductivity. Three-dimensional foams with high ligament thermal conductivity offer a potential solution to the two aforementioned problems but are traditionally fabricated through expensive and/or complex manufacturing methods. Here, laser induced graphene foams, fabricated through a simple and cost effective laser ablation method, are infiltrated with poly(3-hexylthiophene) in a step-wise fashion to demonstrate the impact of polymer on the thermal conductivity of the composite system. Surprisingly, the addition of polymer results in a drastic (250%) improvement in material thermal conductivity, enhancing the graphene foams thermal conductivity from 0.68 W/m-K to 1.72 W/m-K for the fully infiltrated comp...

Direct visualization of thermal conductivity suppression due to enhanced phonon scattering near individual grain boundaries

Understanding the impact of lattice imperfections on nanoscale thermal transport is crucial for diverse applications ranging from thermal management to energy conversion. Grain boundaries (GBs) are ubiquitous defects in polycrystalline materials, which scatter phonons and reduce thermal conductivity (κ). Historically, their impact on heat conduction has been studied indirectly through spatially averaged measurements, that provide little information about phonon transport near a single GB. Here, using spatially resolved time-domain thermoreflectance (TDTR) measurements in combination with electron backscatter diffraction (EBSD), we make localized measurements of κ within few μm of individual GBs in boron-doped polycrystalline diamond. We observe strongly suppressed thermal transport near GBs, a reduction in κ from ∼1000 W m-1 K-1 at the center of large grains to ∼400 W m-1 K-1 in the immediate vicinity of GBs. Furthermore, we show that this reduction in κ is measured up to ∼10 μm away from a GB. A theoretical model is proposed that captures the local reduction in phonon mean-free-paths due to strongly diffuse phonon scattering at the disordered grain boundaries. Our results provide a new framework for understanding phonon-defect interactions in nanomaterials, with implications for the use of high-κ polycrystalline materials as heat sinks in electronics thermal management.

Thermal Conductance of Poly(3-methylthiophene) Brushes

A wide variety of recent work has demonstrated that the thermal conductivity of polymers can be improved dramatically through the alignment of polymer chains in the direction of heat transfer. Most of the polymeric samples exhibit high conductivity in either the axial direction of a fiber or in the in-plane direction of a thin film, while the most useful direction for thermal management is often the cross-plane direction of a film. Here we show poly(3-methylthiophene) brushes grafted from phosphonic acid monolayers using surface initiated polymerization can exhibit through-plane thermal conductivity greater than 2 W/(m K), a 6-fold increase compared to spin-coated poly(3-hexylthiophene) samples. The thickness of these films (10-40 nm) is somewhat less than that required in most applications, but the method demonstrates a route toward higher thermal conductivity in covalently grafted, aligned polymer films.

Probing Growth-Induced Anisotropic Thermal Transport in High-Quality CVD Diamond Membranes by Multifrequency and Multiple-Spot-Size Time-Domain Thermoreflectance

The maximum output power of GaN-based high-electron mobility transistors is limited by high channel temperature induced by localized self-heating, which degrades device performance and reliability. Chemical vapor deposition (CVD) diamond is an attractive candidate to aid in the extraction of this heat and in minimizing the peak operating temperatures of high-power electronics. Owing to its inhomogeneous structure, the thermal conductivity of CVD diamond varies along the growth direction and can differ between the in-plane and out-of-plane directions, resulting in a complex three-dimensional (3D) distribution. Depending on the thickness of the diamond and size of the electronic device, this 3D distribution may impact the effectiveness of CVD diamond in device thermal management. In this work, time-domain thermoreflectance is used to measure the anisotropic thermal conductivity of an 11.8 μm-thick high-quality CVD diamond membrane from its nucleation side. Starting with a spot-size diameter larger than the thickness of the membrane, measurements are made at various modulation frequencies from 1.2 to 11.6 MHz to tune the heat penetration depth and sample the variation in thermal conductivity. We then analyze the data by creating a model with the membrane divided into ten sublayers and assume isotropic thermal conductivity in each sublayer. From this, we observe a two-dimensional gradient of the depth-dependent thermal conductivity for this membrane. The local thermal conductivity goes beyond 1000 W/(m K) when the distance from the nucleation interface only reaches 3 μm. Additionally, by measuring the same region with a smaller spot size at multiple frequencies, the in-plane and cross-plane thermal conductivities are extracted. Through this use of multiple spot sizes and modulation frequencies, the 3D anisotropic thermal conductivity of CVD diamond membrane is experimentally obtained by fitting the experimental data to a thermal model. This work provides an improved understanding of thermal conductivity inhomogeneity in high-quality CVD polycrystalline diamond that is important for applications in the thermal management of high-power electronics.

Thermal conductivity measurements on suspended diamond membranes using picosecond and femtosecond time-domain thermoreflectance

We report on the room temperature in-plane thermal conductivity measurements on a 1-micrometer thick suspended diamond membrane grown by chemical vapor deposition using two different time domain thermoreflectance (TDTR) setups. The first setup is at Stanford University and the second is at Georgia Institute of Technology. Despite the differences between the two setups and the difficulty associated with diamond membranes thermal measurements, we demonstrate excellent repeatability from each setup and a very good agreement between the two setups. The paper outlines steps considered by both groups to minimize the measurement uncertainty and achieve such agreement. The measurement results show that the thermal conductivity displays a large variability across the membrane. The sensitivity and uncertainty analyses suggest that this variability could be a result of the nonuniformity in the diamond and aluminum coating thicknesses across the sample.