Development and Characterization of Thermally Conductive Polymeric Composites for Electronic Packaging Applications
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Development and Characterization of Thermally Conductive Polymeric Composites for Electronic Packaging Applications by Ellen H. Chan A thesis submitted in conformity with the requirements for the degree of Master of Applied Science and Engineering Graduate Department of Mechanical & Industrial Engineering University of Toronto Copyright © 2011 by Ellen H. Chan Abstract Development and Characterization of Thermally Conductive Polymeric Composites for Electronic Packaging Applications Ellen H. Chan Master of Applied Science and Engineering Graduate Department of Mechanical & Industrial Engineering University of Toronto 2011 Advancements in the semiconductor industry have lead to the miniaturization of components and increased power densities, resulting in thermal management issues. Due to this shift, finding multifunctional materials with excellent thermal conductivity and electrical resistivity are becoming increasingly important. For this research thesis, thermally conductive polymer composites were developed and characterized. In the first study, a LLDPE matrix was combined with hBN and SiC to determine the effects of both filler type and filler content. Novel porous composite materials were also fabricated to align thermally conductive fillers, improving ke f f while significantly reducing the overall weight. In the second study, PPS was used as a high performance matrix material and combined with different types of hBN to investigate the effects of size, shape, and aspect ratio on the composite, as well as the effect of hybrid fillers. The composites were characterized with respect to their physical, thermal, electrical, and mechanical properties. ii Acknowledgements I would like to first and foremost thank my co-supervisors Dr. Hani E. Naguib and Dr. Francis Dawson for the opportunity to conduct my masters as a part of their laboratories. Their guidance and mentorship throughout the duration of the project was greatly appreciated. I would also like to thank my fellow SAPLings (and DUMPLings) for all of the support and assistance they provided me with over the two years. Thank you for offering an immense amount of help when I would claim to have ”broken science”. I would like to especially thank Sunny Leung for coordinating our project and ensuring we were always on track. My other colleuges: Aaron Price, Linus Leung, Christine Chan, Reza Rizvi, Eunji In, Choonghee Jo, Dina Badawy, Shahrzad Ghaffari, and Omer Khan. To my family and friends. Thank you very much for keeping me sane, always encouraging and constantly reassuring me that the seemingly endless amount of work would all get done. My friends, thank you for keeping my mind stimulated, my belly full, and my body pumped full of caffeine. Most importantly, I would thank my family: Mom, Dad, Laura, Teresa, Herman, and Vivi, for always lending an ear, providing me with sound reasoning and a level headed opinion, and always having confidence in my abilities. Without all of you I would not have succeeded. iii Contents 1 Introduction 1 1.1 ElectronicPackagingMaterials . 2 1.2 ThesisObjectives ................................ 3 1.3 ThesisOrganization............................... 4 2 Background and Literature Survey 6 2.1 ElectronicPackaging .............................. 6 2.2 ThermallyConductiveMaterials . 8 2.3 ElectricallyInsulatingMaterials. 11 2.4 Polymer/CeramicComposites. 12 2.4.1 FabricationMethods . 13 2.4.2 CommonIssues............................. 13 2.4.3 LessonsLearned ............................ 14 2.5 FoamedCompositeMaterials . 15 2.6 MicromechanicalModelling . 17 2.6.1 Basic Models: Series, Parallel and Geometric Mean Models.... 18 2.6.2 Maxwell Theoretical Model . 19 2.6.3 Bruggeman Theoretical Model . 19 2.6.4 Lewis and Nielsen Theoretical Model . 19 2.7 Summary..................................... 20 iv 3 Fabrication and Characterization 22 3.1 MaterialSelection................................ 22 3.1.1 MatrixMaterials ............................ 22 3.1.2 FillerMaterials ............................. 23 3.2 FabricationTechniques . 25 3.2.1 Melt-BlendProcess . 25 3.2.2 Dry-BlendProcess ........................... 27 3.3 CharacterizationTechniques. 27 3.3.1 ThermalProperties. 27 3.3.2 ElectricalProperties . 29 3.3.3 MechanicalProperties . 30 3.3.4 Morphology............................... 30 4 LLDPE Based Composites 34 4.1 The Effect of DifferentTypesofFiller . 34 4.1.1 ThermalProperties. 35 4.1.2 ElectricalProperties . 38 4.1.3 MechanicalProperties . 39 4.1.4 Morphology............................... 42 4.1.5 MicromechanicalModelling. 45 4.1.6 Summary ................................ 49 4.2 The EffectofContent .............................. 49 4.2.1 ThermalProperties. 50 4.2.2 ElectricalProperties . 51 4.2.3 MechanicalProperties . 53 4.2.4 Morphology............................... 55 4.2.5 MicromechanicalModelling. 55 4.2.6 Summary ................................ 59 v 4.3 ComparisonofMixingTechniques . 60 4.4 The EffectofPorosity.............................. 61 4.4.1 Morphology............................... 63 4.4.2 ThermalConductivity . 70 4.4.3 Summary ................................ 73 5 PPS Based Composites 77 5.1 The EffectofFillerSizeandShape . 77 5.1.1 ThermalProperties. 78 5.1.2 ElectricalProperties . 80 5.1.3 MechanicalProperties . 80 5.1.4 Morphology............................... 84 5.1.5 MicromechanicalModelling. 84 5.1.6 Summary ................................ 88 5.2 The EffectofHybridFillers .......................... 88 5.2.1 ThermalProperties. 89 5.2.2 ElectricalProperties . 91 5.2.3 MechanicalProperties . 91 5.2.4 Morphology............................... 96 5.2.5 Summary ................................ 96 5.3 ComparisonofMatrixMaterials . 98 5.3.1 MicromechanicalModelling. 100 5.4 OtherStudies ..................................101 5.4.1 The EffectofaCouplingAgent . .101 6 Conclusions and Recommendations 106 6.1 Conclusions ...................................106 6.2 Recommendations ...............................109 vi Bibliography 111 vii List of Tables 2.1 Thermal conductivity (k)-values of common materials at room temper- ature. ....................................... 10 3.1 Physical Properties of the Matrix Materials . 26 3.2 Physical Properties of the Filler Materials. ...... 26 4.1 LLDPE-hBN-SiCCompositions . 36 4.2 PorousLLDPE-hBNCompositions . 64 5.1 PPS-hBNHybridCompositions . 89 5.2 Comparison between PPS and LLDPE Matrix Materials on k ....... 99 5.3 TGA analysis of hBN weight loss upon heating to 900 °C . 105 viii List of Figures 1.1 Schematic of modified heat sink to include electrically resistive composite. 3 2.1 Examples of types of electronic packaging, (a) integrated circuits (b) electronic chips (c) liquid epoxy encapsulation [1]. .... 8 2.2 Electrical conductivity (S/cm).......................... 12 3.1 Variations of Boron Nitride. (a) PTX25, (b) PTX60, (c) PT371, and (d) PT110. ...................................... 26 3.2 Flow Chart of Composite Processing. 28 3.3 Thermal Conductivity Analyzer Setup. 33 4.1 Thermal conductivity (k) of LLDPE-hBN-SiC composites. 36 4.2 Coefficient of thermal expansion (CTE) of LLDPE-hBN-SiC composites. 38 4.3 Electrical properties of LLDPE-hBN-SiC composites. ....... 40 4.4 Compressive elastic modulus (E) of LLDPE-hBN-SiC composites. 43 4.5 Compressive strength (σy) of LLDPE-hBN-SiC composites. 43 4.6 SEM Images of LLDPE-based composites containing (a) 2.46VF SiC (b) 5.34VF SiC, (c) 9.36VF SiC (d) 33.3VF SiC . 44 4.7 LLDPE-33VF SiC at 350× magnification. 44 4.8 SEM images of LLDPE-based composites containing (a) 2.46VF hBN (b) 5.34VF hBN, (c) 9.36VF hBN (d) 33.3VF hBN. 46 4.9 LLDPE-33VF hBN at 1,500× magnification. 46 ix 4.10 SEM images of LLDPE-based composites containing 33VF hBN and (a) 2.46VF SiC (b) 5.34VF SiC, (c) 9.36VF SiC at 100× magnification, and (d) 9.36VF SiC at 350× magnification.. 47 4.11 Theoretical predictions compared to experimental data for the effect of differentfillers(a)hBN,and(b)SiC. 48 4.12 Thermal conductivity (k) of LLDPE-hBN composites with varying filler content....................................... 52 4.13 Coefficient of thermal expansion (CTE) of LLDPE-hBN composites with varyingfillercontent............................... 52 4.14 Electrical properties of LLDPE-hBN composites with varying filler con- tent. (a) electrical impedance, and (b) electrical conductivity. ...... 54 4.15 Elastic compressive modulus (E) of LLDPE-hBN composites with vary- ingfillercontent. ................................ 56 4.16 Compressive strength (σy) of LLDPE-hBN composites with varying filler content....................................... 56 4.17 SEM Images of LLDPE-hBN composites with different filler content at varyingmagnifications. 57 4.18 Theoretical predictions compared to experimental data for the effect of contentstudy. .................................. 59 4.19 Thermal Conductivity (k) of LLDPE-hBN composites fabricated using variousprocessingtechniques. 62 4.20 SEM Images of LLDPE Foamed Composites with varying amounts of microspheres, containing 33 vol.% with 20 and 40 void percent. 66 4.21 SEM Images of LLDPE Foamed Composites with varying amounts of microspheres, containing 50 vol.% with 20 and 40 void percent. 67 4.22 SEM Images of LLDPE Foamed Composites with varying residence time, containing 33 vol.% with 20 and 40 void percent. 68 x 4.23 SEM Images of LLDPE Foamed Composites with varying residence time, containing 50 vol.% with 20 and 40 void percent. 69 4.24 SEM Images of LLDPE Foamed Composites with 1.5× the calculated amount of Expancel necessary to fill 20 void% at (a) 250×, and (b) 1,000×