<p dir="ltr">This work investigates four aspects of Ga-based low melting temperature alloys in their role as TIMs: the interaction between Ga and metal substrates, the change in the thermodynamic behavior of the liquid metal alloy, the evolution of the thermal performance, and mitigation strategies against Ga corrosion.</p>

The development of wide band gap semiconductors for power and RF electronics as well as high power silicon microelectronics has pushed the need for advanced thermal management techniques to ensure device reliability. While many techniques to remove large heat fluxes from devices have been developed, fewer advancements have been made in the development of new materials which can be integrated into the packaging architecture. This is especially true in the development of thermal interface materials. Conventional solders are currently being used for interface materials in the most demanding applications, but have issues of high cost, long term reliability and inducing negative thermomechanical effects in active die. Carbon nanotubes have been suggested as a possible thermal interface material which can challenge solders because of their good thermal properties and 1-D structure which can enhance mechanical compliance between surfaces. In this work, we have developed a novel growth and transfer printing method to manufacture vertically aligned CNTs for thermal interface applications. This method follows the nanomaterial transfer printing methods pioneered at Georgia Tech over the past several years. This process is attractive as it separates the high growth synthesis temperatures from the lower temperatures needed during device integration. For this thesis, CNTs were grown on oxidized Si substrates which allowed us to produce high quality vertically aligned CNTs with specific lengths. Through the development of a water vapor assisted etch process, which takes place immediately after CNT synthesis, control over the adhesion of the nanotubes to the growth surface was achieved. By controlling the adhesion we demonstrated the capability to transfer arrays of vertically aligned CNTs to polyimide tape. The CNTs were then printed onto substrates like Si and Cu using a unique gold bonding process. The thermal resistances of the CNTs and the bonded interfaces were measured using the photoacoustic method, and the strength of the CNT interface was measured through tensile tests. Finally, the heat dissipation capabilities of the vertically aligned CNTs were demonstrated through incorporation with high brightness LEDs. A comparison of LED junction temperatures for devices using a CNT and lead free solder thermal interface was made.

Shrinking volume, coupled with higher performance, microprocessors and integrated circuits have led to serious heat dissipation issues. In an effort to mitigate the excessive amounts of waste heat and ensure electronic survivability, heat sinks and spreaders are incorporated into heat generating device structures. This inevitability creates a thermal pathway through an interface. Thermal interfaces can possess serious thermal resistances for heat conduction. The introduction of a thermal interface material (TIM) can drastically increase the thermal performance of the component. Exceptional thermal properties of multiwall carbon nanotubes (MWCNTs) have spurred interest in their use as TIMs. MWCNTs inherently grow in vertically-oriented, high aspect ratio arrays, which is ideal in thermal interface applications because CNTs posses their superior thermal performance along their axis. In this paper, laser flash thermal characterization of sandwich‐bonded and cap‐screw‐bonded aluminum discs for both adhesive-infiltrated and “dry”, 100% MWCNT arrays, respectively. Thermal contact resistances as low as 18.1 mm2K/W were observed for adhesive‐infiltrated arrays and, even lower values, down to 10.583 mm2K/W were measured for “dry” MWCNT arrays. The improved thermal performance of the arrays compared to thermal adhesives and greases currently used in the electronics and aerospace industries, characterize MWCNT arrays as a novel, lighter‐weight, non‐corrosive replacement.

High performance/small package electronics create difficult thermal issues for integrated circuits. Challenges exist at material interfaces due to interfacial contact resistances. Multiwall carbon nanotube (MWCNT) arrays are considered to be excellent candidates for use as thermal interface materials (TIMs) due to outstanding thermal/mechanical properties. In this work, MWCNT array TIMs are analyzed in aluminum and carbon fiber composites via flash diffusivity analysis. The effect of TIM thickness, areal/bulk density, surface cleanliness, and volumetric packing fraction; along with the effect of substrate finish and interfacial contact pressure on thermal performance are analyzed. Trends show the best TIMs possess low thickness, high bulk density and packing fraction, and clean surfaces. Pressure dramatically increases thermal performance after establishing contact, with diminishing returns from additional pressure. Diffusivities approaching 40 mm2/s and 0.65 mm2/s are recorded for aluminum and composite systems. Oxygen plasma etching and high temperature annealing (“Graphitizing”) are investigated as methods to remove amorphous carbon from array surfaces. Graphitized TIMs report diffusivity improvements up to 53.8%. Three methods of incorporating MWCNTs into composites are attempted for thermal/mechanical property enhancement. Conductance calculations show increasing diffusivity without increasing thickness enhances thermal performance in composites. MWCNTs for mechanical property enhancement produce no change, or detrimental effects.

abstract: Soft polymer composites with improved thermal conductivity are needed for the thermal management of electronics. Interfacial thermal boundary resistance, however, prevents the efficient use of many high thermal conductivity fill materials. Magnetic alignment of ferrous fill material enforces percolation of the high thermal conductivity fill, thereby shifting the governing boundary resistance to the particle- particle interfaces and increasing the directional thermal conductivity of the polymer composite. Magnetic alignment maximizes the thermal conductivity while minimizing composite stiffening at a fill fraction of half the maximum packing factor. The directional thermal conductivity of the composite is improved by more than 2-fold. Particle-particle contact engineering is then introduced to decrease the particle- particle boundary resistance and further improve the thermal conductivity of the composite. The interface between rigid fill particles is a point contact with very little interfacial area connecting them. Silver and gallium-based liquid metal (LM) coatings provide soft interfaces that, under pressure, increase the interfacial area between particles and decrease the particle-particle boundary resistance. These engineered contacts are investigated both in and out of the polymer matrix and with and without magnetic alignment of the fill. Magnetically aligned in the polymer matrix, 350nm- thick silver coatings on nickel particles produce a 1.8-fold increase in composite thermal conductivity over the aligned bare-nickel composites. The LM coatings provide similar enhancements, but require higher volumes of LM to do so. This is due to the rapid formation of gallium oxide, which introduces additional thermal boundaries and decreases the benefit of the LM coatings. The oxide shell of LM droplets (LMDs) can be ruptured using pressure. The pressure needed to rupture LMDs matches closely to thin-walled pressure vessel theory. Furthermore, the addition of tungsten particles stabilizes the mixture for use at higher pressures. Finally, thiols and hydrochloric acid weaken the oxide shell and boost the thermal performance of the beds of LMDs by 50% at pressures much lower than 1 megapascal (MPa) to make them more suitable for use in TIMs. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2019

This thesis describes the synthesis of a low modulus, thermally conductive thermal interface materials (TIM) using metal decorated nanotubes as fillers. TIMs are very important in electronics because they act as a thermally-conductive medium for thermal transfer between the interface of a heat sink and an electronic package. The performance of an electronic package decreases with increasing operating temperature, hence, there exists a need to create a TIM which has high thermal conduction to reduce the operating temperature. The TIM in this study is made from metal decorated multi-walled carbon nanotubes (MWCNT) and Vinnapas®BP 600 polymer. The sample was functionalized using mild oxidative treatment with nitric acid (HNO3) or, with N-Methly-2-Pyrrolidone (NMP). The metals used for this experiment were copper (Cu), tin (Sn), and nickel (Ni). The metal nanoparticles were seeded using functionalized MWCNTs as templates. Once seeded, the nanotubes and polymer composites were made with or without sodium dodecylbenzene sulfonate (SDBS), as a surfactant. Thermal conductivity (k) measurement was carried out using ASTM D-5470 method at room temperature. This setup best models the working conditions of a TIM. The TIM samples made for this study showed promise in their ability to have significant increase in thermal conduction while retaining the polymer’s mechanical properties. The highest k value that was obtained was 0.72 W/m-K for a well dispersed aligned 5 wt percent Ni@MWCNT sample. The Cu samples underperformed both Ni and Sn samples for the same synthesis conditions. This is because Cu nanoparticles were significantly larger than those of Ni and Sn. They were large enough to cause alloy scattering and too large to attach to the nanotubes. Addition of thermally-conductive fillers, such as exfoliated graphite, did not yield better k results as it sunk to the bottom during drying. The use of SDBS greatly increased the k values of the sample by reducing agglomeration. Increasing the amount of metal@MWCNT wt percent in the sample had negative or no effect to the k values. Shear testing on the sample shows it adheres well to the surface when pressure is applied, yet it can be removed with ease.

To fulfill the potential of carbon nanotube (CNT) as thermal interface material (TIM), the packing density of CNT array needs improvement. In this work, two potential ways to increase the packing density of CNT array are tested. They are liquid precursor(LP)CVD and cycled catalyst deposition method. Although LP-CVD turned out to be no help for packing density increase, it is proved to enhance the CNT growth rate. The packing density of CNT array indeed increases with the cycle number. The thermal conductivity of the CNT array increases with the packing density. This work is believed to be a step closer to the real life application of CNT in electronic packaging industry.

We design a facile approach to investigate the role benzene derivatives play in the capacitance enhancement of graphene-based supercapacitors. The main reason is attributed to the pseudocapacitance of the aromatic molecules rather than the former one. Meanwhile, we find that the para and ortho substituted benzene derivatives contribute much more than the meta substituted ones. In addition, we fabricate an all-solid-state flexible MSC based on metal-reduced GO. The as-fabricated MSC shows high areal capacitance and excellent reliability, which makes it a promising energy storage candidate for wearable electronics. Based on the work of MSC, we achieve a flexible ac line-filter that is not only competitive against commercial product but also suitable for mass production. Meanwhile, we produce a three-dimensional graphene/polydimethylsiloxane composite that gives a thermal resistance as small as 14 mm2K/W, which is comparable to commercial products. What’s more, a convenient transient program that saves much time is developed to measure the thermal resistance.

Thesis (M.S.)--State University of New York at Binghamton, Thomas J. Watson School of Engineering and Applied Science, Department of Mechanical Engineering, 2009. / Includes bibliographical references.

abstract: Advancements in thermal interface materials (TIMs) allows for the creation of new and more powerful electronics as they increase the heat transfer from the component to the heat sink. Current industrial options provide decent heat transfer, but the creation of TIMs with higher thermal conductivities is needed. In addition, if these TIMs are elastic in nature, their effectiveness can greatly increase as they can deal with changing interfaces without degradation of their properties. The research performed delves into this idea, creating elastic TIMs using liquid metal (LM), in this case galinstan, along with other matrix particles embedded in Polydimethylsiloxane (PDMS) to create an easy to use, relatively inexpensive, thermally conductive, but electrically insulative, pad with increased thermal conductivity from industrial solutions. The pads were created using varying amounts of LM and matrix materials ranging from copper microspheres to diamond powder mixed into PDMS using a high-speed mixer. The material was then cast into molds and cured to create the pads. Once the pads were created, the difficulty came in quantifying their thermal properties. A stepped bar apparatus (SBA) following ASTM D5470 was created to measure the thermal resistance of the pads but it was determined that thermal conductivity was a more usable metric of the pads’ performance. This meant that the pad’s in-situ thickness was needed during testing, prompting the installation of a linear encoder to measure the thickness. The design and analysis of the necessary modification and proposed future design is further detailed in the following paper. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2017