Electrically Nonconductive Thermal Pastes with Carbon as the Thermally Conductive Component

Electrically nonconductive thermal pastes have been attained using carbon (carbon black or graphite) as the conductive component and ceramic (fumed alumina or exfoliated clay) as the nonconductive component. For graphite particles (5 μm), both clay and alumina are effective in breaking up the electrical connectivity, resulting in pastes with electrical resistivity up to 10¹³Ω·cm and thermal contact conductance (between copper surfaces of roughness 15 μm) up to 9 × 10⁴ W/m²·°C. For carbon black (30 nm), clay is more effective than alumina, providing a paste with resistivity 10¹¹ Ω·cm and thermal contact conductance 7 × 10⁴ W/m²·°C. Carbon black increases the thermal stability, whereas either graphite or alumina decreases the thermal stability. The antioxidation effect of carbon black is further increased by the presence of clay up to 1.5 vol.%. The addition of clay (up to 0.6 vol.%) or alumina (up to 2.5 vol.%) to graphite paste enhances the thermal stability.     

Nanoclay Paste as a Thermal Interface Material for Smooth Surfaces

A paste in the form of a polyol ester vehicle (liquid) containing 0.6 vol.% nanoclay is an effective thermal interface material. Nanoclay with a high conformability and hence a small bond line thickness is preferred, namely montmorillonite containing a quarternary ammonium salt organic modifier (dimethyl dehydrogenated tallow) at 125 meq/100 g clay, after exfoliation by using the vehicle. When it is used between smooth (0.009 μm) copper surfaces at a pressure of 0.69 MPa, the thermal contact conductance reaches 40 × 10⁴ W/m² K, in contrast to the corresponding values of 28 × 10⁴ W/m² K, 28 × 10⁴ W/m² K, 25 × 10⁴ W/m² K, and 24 × 10⁴ W/m² K previously reported for carbon black, fumed alumina, fumed zinc oxide, and graphite nanoplatelet pastes. Between rough copper surfaces (12 μm), the conductance provided by the nanoclay paste is slightly below those of the other pastes. The superiority of the nanoclay paste for smooth surfaces is attributed to the␣submicron bond line thickness; the inferiority for rough surfaces is due to the low thermal conductivity. The conductance provided by the nanoclay paste increases from 31 × 10⁴ W/m² K to 40 × 10⁴ W/m² K when the pressure is increased from 0.46 MPa to 0.92 MPa. This pressure dependence is stronger than that of any of the other pastes studied.     

Carbon-black thixotropic thermal pastes for improving thermal contacts

This paper addresses thermal interface materials for thermal conduction of excess heat for microelectronic applications. Carbon black (30 nm) thixotropic paste based on polyol ethers is comparable to carbon black fluidic paste based on polyethylene glycol (PEG) in its effectiveness as a thermal paste, and in its dependence on pressure history. Prior pressure (up to 0.69 MPa) application is helpful. The optimum carbon black content is 2.4 vol.% for the thixotropic paste. The thermal contact conductance across copper surfaces is 30 × 10⁴ and 11 × 10⁴ W/m²-°C for surface roughness of 0.05 μm and 15 μm, respectively. The volume electrical resistivity is 3 × 10³ Ω-cm. Boron nitride (BN) (5–11 μm) and graphite (5 μm) thixotropic pastes are less effective than carbon black thixotropic paste by up to 70% and 25%, respectively, in thermal contact conductance, due to low conformability.     

Thermal and Structural Characterizations of Individual Single‐, Double‐, and Multi‐Walled Carbon Nanotubes

Thermal conductance measurements of individual single‐ (S), double‐ (D), and multi‐ (M) walled (W) carbon nanotubes (CNTs) grown using thermal chemical vapor deposition between two suspended microthermometers are reported. The crystal structure of the measured CNT samples is characterized in detail using transmission electron microscopy (TEM). The thermal conductance, diameter, and chirality are all determined on the same individual SWCNT. The thermal contact resistance per unit length is obtained as 78–585 m K W^?1 for three as‐grown 10–14 nm diameter MWCNTs on rough Pt electrodes, and decreases by more than 2 times after the deposition of amorphous platinum–carbon composites at the contacts. The obtained intrinsic thermal conductivity of approximately 42–48, 178–336, and 269–343 W m^?1 K^?1 at room‐temperature for the three MWCNT samples correlates well with TEM‐observed defects spaced approximately 13, 20, and 29 nm apart, respectively; whereas the effective thermal conductivity is found to be limited by the thermal contact resistance to be about 600 W m^?1 K^?1 at room temperature for the as‐grown DWCNT and SWCNT samples without the contact deposition.     

Comparative evaluation of thermal interface materials for improving the thermal contact between an operating computer microprocessor and its heat sink

Testing of the relative effectiveness of various thermal interface materials for improving the thermal contact between the well-aligned mating surfaces of an operating computer microprocessor (with an integrated heat spreader) and its heat sink shows that carbon black paste, whether by itself or as a coating on aluminum or flexible graphite, is more effective than silver paste (Arctic Silver), but is comparable in effectiveness to aluminum paste (Shin-Etsu). The carbon black paste by itself is as effective as the Shin-Etsu paste coated aluminum. The Shin-Etsu paste is more effective than Arctic Silver, whether by itself or as a coating. The relative performance is mostly consistent with that assessed by measuring the thermal contact conductance. The correlation is particularly strong for conductance below 3×10⁴ W/m²·°C. The discrepancy is attributed to the difference in surface roughness between computer and guarded hot plate surfaces. In the case in which the mating surfaces of microprocessor and heat sink are not well aligned, Shin-Etsu and Arctic Silver are more effective than carbon black.     

Nanostructured Interfaces for Thermoelectrics

Temperature drops at the interfaces between thermoelectric materials and the heat source and sink reduce the overall efficiency of thermoelectric systems. Nanostructured interfaces based on vertically aligned carbon nanotubes (CNTs) promise the combination of mechanical compliance and high thermal conductance required for thermoelectric modules, which are subjected to severe thermomechanical stresses. This work discusses the property require- ments for thermoelectric interface materials, reviews relevant data available in the literature for CNT films, and characterizes the thermal properties of vertically aligned multiwalled CNTs grown on a candidate thermoelectric material. Nanosecond thermoreflectance thermometry provides thermal property data for 1.5-μm-thick CNT films on SiGe. The thermal interface resistances between the CNT film and surrounding materials are the dominant barriers to thermal transport, ranging from 1.4 m² K MW⁻¹ to 4.3 m² K MW⁻¹. The volumetric heat capacity of the CNT film is estimated to be 87 kJ m⁻³ K⁻¹, which corresponds to a volumetric fill fraction of 9%. The effect of 100 thermal cycles from 30°C to 200°C is also studied. These data provide the groundwork for future studies of thermoelectric materials in contact with CNT films serving as both a thermal and electrical interface.     

A Promising Radiation Thermal Protection Coating Based on Lamellar Porous Ca-Cr co-Doped Y3NbO7 Ceramic

Dissipation of heat efficiently from a hot object via radiation while minimizing the inward heat conduction is the key requirement of radiation thermal protection. In this study, a Ca-Cr co-doped Y₃NbO₇ coating with lamellar porous structure is fabricated, which shows an ultra-low thermal conductivity (<0.7 W m⁻¹ K⁻¹) and near-unity emissivity (>0.9) across a broad wavelength range of ≈1–24 µm. This record high emissivity to thermal conductivity ratio (≈1.3) is experimentally and theoretically revealed from a multi-scale perspective. The diffusoin-mediated thermal conduction feature of niobates combined with lamellar porous structure of the coating reduces its thermal conductivity to an impressive 0.5 W m⁻¹ K⁻¹ at 25 °C, surpassing the theoretical amorphous limitation of 0.72 W m⁻¹ K⁻¹. Experiments and FDTD calculation results demonstrate that the intrinsic emissivity dips at shallow extinction wavelengths (1 and 8 µm) and strong phonon-polariton resonances wavelengths (>13 µm) can be effectively compensated by the multiple scattering/absorption and gradual modulation of conical shape/effective refractive index induced by surface micro-protrusion structures, respectively. Furthermore, the coating exhibits robust mechanical and thermal stability with a high bonding strength (18.3 MPa) and thermal expansion coefficient (≈11 × 10⁻⁶ K⁻¹ at 1200 °C) comparable to YSZ, showing great potential in the radiation thermal protection field.     

A Thermally Conductive Composite with a Silica Gel Matrix and Carbon-Encapsulated Copper Nanoparticles as Filler

Core–shell-structured nanocapsules with a copper core encapsulated in a carbon shell (Cu-C) were synthesized by a direct-current arc-discharge method. Morphological and microstructural characterization showed that the Cu-C consisted of a nanosized Cu core and carbon shell, with the carbon shells containing 6 to 15 ordered graphitic layers and amorphous carbon that effectively shield the metallic Cu core from oxidation. A thermally conductive composite was successfully fabricated using a silica gel matrix incorporated with Cu-C filler. The Cu-C nanoparticles were homogeneously dispersed in the silica gel. The effects of Cu-C on the thermal conductivity, electrical resistivity, and coefficient of thermal expansion (CTE) of the composite were investigated. For composites with 6.16 vol.%, 11.04 vol.%, 16.70 vol.%, and 23.34 vol.% Cu-C content, the thermal conductivity at 50°C was 0.32 W/(m K) to 0.77 W/(m K), the electrical resistivity was 1.98 × 10⁹, 3.48 × 10⁷, 302, and 1 Ω m, respectively, while the CTE at 200°C was 3.79 × 10^?4 K^?1 to 3.44 × 10^?4 K^?1. The results reveal that the ordered graphitic shells in the Cu-C increased both the thermal and electrical conduction, but decreased the CTE by preventing the Cu cores from expanding.     

Current flow mechanism in ohmic contact to <Emphasis Type="Italic">n</Emphasis>-4<Emphasis Type="Italic">H</Emphasis>-SiC

Current flow in an In-n-4H-SiC ohmic contact (n ≈ 3 × 10¹⁷ cm⁻³) has been studied by analyzing the temperature dependence of the per-unit-area contact resistance. It was found that the thermionic emission across an ∼0.1-eV barrier is the main current flow mechanism and the effective Richardson constant is ∼2 × 10⁻² A cm⁻² K⁻¹.     

Pd-Ge contact to n-GaAs with the TiW diffusion barrier

Pd-Ge based ohmic contact to n-GaAs with a TiW diffusion barrier was investigated. Electrical analysis as well as Auger electron spectroscopy and the scanning electron microscopy were used to study the contact after it was subjected to different furnace and rapid thermal annealing and different aging steps. All analyses show that TiW can act as a good barrier metal for the Au/Ge/Pd/n-GaAs contact system. A value of 1.45 × 10⁻⁶ Ω-cm² for the specific contact resistance was obtained for the Au/TiW/Ge/Pd/n-GaAs contact after it was rapid thermally annealed at 425°C for 90 s. It can withstand a thermal aging at 350°C for 40 h with its ρ_c increasing to 2.94 × 10⁻⁶Ω-cm² and for an aging at 410°C for 40 h with its ρ_c increasing to 1.38 × 10⁻⁵ Ω-cm².     

Halogen lamp rapid thermal annealing of Si- and Be-implanted In0.53Ga0.47As

Halogen lamp rapid thermal annealing was used to activate 100 keV Si and 50 keV Be implants in In_0.53Ga_0.47As for doses ranging between 5 × 10¹²−4 × 10¹⁴ cm⁻². Anneals were performed at different temperatures and time durations. Close to one hundred percent activation was obtained for the 4.1 × 10¹³ cm⁻² Si-implant, using an 850° C/5 s anneal. Si in-diffusion was not observed for the rapid thermal annealing temperatures and times used in this study. For the 5 × 10¹³ cm⁻² Be-implant, a maximum activation of 56% was measured. Be-implant depth profiles matched closely with gaussian profiles predicted by LSS theory for the 800° C/5 s anneals. Peak carrier concentrations of 1.7 × 10¹⁹ and 4 × 10¹⁸ cm⁻³ were achieved for the 4 × 10¹⁴ cm⁻² Si and Be implants, respectively. For comparison, furnace anneals were also performed for all doses.     

Pressure electrical contact improved by carbon black paste

Pressure and pressureless electrical contacts were evaluated by measuring the contact electrical resistivity between copper mating surfaces. Pressure electrical contacts with a contact resistivity of 2×10⁻⁵ Ω·cm² have been attained using a carbon black paste of a thickness of less than 25 μm as the interface material. In contrast, a pressureless contact with silver paint as the interface material exhibits a higher resistivity of 3×10⁻⁵ Ω·cm² or above. A pressureless contact with colloidal graphite as the interface material exhibits the same high contact resistivity (1×10⁻⁴ Ω·cm²) as a pressure contact without any interface material. On the other hand, pressureless contacts involving solder and silver epoxy exhibit lower contact resistivity than carbon black pressure contacts.     

Pt and W ohmic contacts to p-6H-SiC by focused ion beam direct-write deposition

Low resistance Pt and W ohmic metallizations to p-type 6H-SiC, using focused ion beam (FIB) surface-modification and in-situ direct-write metal deposition without annealing, are reported. FIB (Ga) surface-modification and in-situ deposition of Pt, and W showed minimum contact resistance values of 2.8 × 10⁻⁴ ohm-cm² to 2.5 × 10⁻⁴ ohm-cm², respectively. A comparison with ex-situ pulse laser deposited Pt on surface-modified areas showed comparable contact resistance values and similar behavior. Auger and secondary ion mass spectroscopy analysis showed a significant (∼4% a.c.) incorporation of Ga within a 15 nm distance from the SiC surface with surface-modification. Atomic force micros-copy studies showed that surface-modification process smooths out the SiC surface significantly.     

Ohmic contact formation on inductively coupled plasma etched 4H-silicon carbide

We report on the investigation of ohmic contact formation using sputtered titanium-tungsten contacts on an inductively coupled plasma (ICP) etch-damaged 4H-SiC surface. Transfer length method (TLM) measurements were performed to characterize how ICP-etch damage affects the performance of ohmic contacts to silicon carbide. In order to recover etch damage, high-temperature oxidation (1250°C for 1 h) was evaluated for one of the samples. Some of the etch damage was recovered, but it did not fully recover the etch damage for the sample etched with medium platen power (60 W). From our TLM measurements, the specific contact resistance (ρ _C of sputtered titanium tungsten on highly doped n⁺-type 4H-SiC epilayers with a doping of 1.1×10¹⁹ cm⁻³ for the unetched reference sample, 30-W etched, and 60-W etched with and without sacrificial oxidation was as low as 3.8×10⁻⁵ Ωcm², 3.3×10⁻⁵ Ωcm², 2.3×10⁻⁴ Ωcm², and 1.3×10⁻³ Ωcm², respectively. We found that the low-power (30 W) ICP-etching process did not affect the formation of ohmic contacts, and we did not observe any difference between the unetched and the 30-W etched sample from our TLM measurements, having the same value of the ρ _C. However, medium-platen-power (60 W) ICP etching showed significant influence on the ohmic contact formation. We found that the specific contact resistance is highly related to the surface roughness and quality of the metals, and the lower, specific contact resistance is due to smoother and denser ohmic contacts.     

Density measurement of Sn-40Pb,Sn-57Bi,and Sn-9Zn by indirect Archimedean method

By the indirect Archimedean method, the density and the density-temperature relationship of the Sn-40Pb eutectic alloy and two Pb-free solders, Sn-57Bi and Sn-9Zn eutectic alloys, were measured from room temperature to about 250°C. The results showed that the density-temperature dependence for each alloy in both solid and melting states can be fitted linearly as ρ_S(Sn-40Pb)=8.51−8.94×10⁻⁴(T−25°C), ρ_L(Sn-40Pb)=8.15−13.8×10⁻⁴(T−T_m); ρ_S(Sn-57Bi)=8.54−5.86 × 10⁻⁴(T−25°C), ρ_L(Sn-57Bi)=8.51−10.9×10⁻⁴(T−T_m); and ρ_s(Sn-9Zn)=7.22−7.78×10⁻⁴(T−25°C), ρ_L(Sn-9Zn)=6.89−5.88×10 ⁻⁴(T−T_m), where the density unit was g/cm³. At the melting point, density of the melt of these solders is 8.15 g/cm³, 8.51 g/cm³, and 6.89 g/cm³, respectively. The density decreased 2.6% for Sn-40Pb eutectic alloy during melting, and 2.7% for Sn-9Zn eutectic alloy, but increased 0.5% for Sn-57Bi eutectic alloy. The excess molar volume for these alloys after mixing at their melting point is 0.03 cm³/mol for Sn-40Pb, 0.09 cm³/mol for Sn-57Bi, and 0.21 cm³/mol for Sn-9Zn.     

Time-independent mechanical and physical properties of the ternary 95.5Sn-3.9Ag-0.6Cu solder

The development of a constitutive model for predicting the thermal-mechanical fatigue (TMF) of 95.5Sn-3.9Ag-0.6Cu (wt.%) Pb-free solder interconnects requires the measurement of time-independent mechanical and physical properties. Yield stress was measured over the temperature range of −25–160°C using strain rates of 4.2 × 10⁻⁵ s⁻¹ and 8.3 × 10⁻⁴ s⁻¹. The yield-stress values ranged from approximately 40 MPa at −25°C to 10 MPa at 160°C for tests performed at 4.2 × 10⁻⁵ s⁻¹. The faster strain rate and specimen aging had a limited impact on the yield stress. The true stress/true strain curves indicated that dynamic-recovery and dynamic-recrystallization processes took place in as-cast samples exposed to temperatures of 125°C and 160°C, respectively, while tested at a strain rate of 4.2 × 10⁻⁵ s⁻¹. Aging the sample prior to testing, as well as a faster strain rate, mitigated both phenomena. Dynamic Young’s modulus values ranged from 55 GPa at −50°C to 35 GPa at 200°C, while the coefficient of thermal expansion (CTE) increased from approximately 12 × 10⁻⁶°C⁻¹ to 24 × 10⁻⁶°C⁻¹ for the same temperature range. The aging treatment had little effect on either Young’s modulus or the CTE.     

Polyol-based phase-change thermal interface materials

Polyol-based phase-change thermal interface materials that exhibit high thermal contact conductance and thermal stability have been developed for microelectronic cooling. By using a diol (polycaprolactone or polyester diol in the form of 2-oxepanone) of molecular weight 1,000–2,000 amu, along with 4 vol.%-hexagonal boron nitride particles, this work attained thermal contact conductance (at 70°C, across copper surfaces) that is higher than that attained by using paraffin wax, polyether glycol, polyethylene glycol, or tetradecanol (in place of the diol) and that attained by commercial phase-change thermal interface materials. The thermal stability of the diol is superior to the other phase change materials mentioned above, although the heat of fusion is lower. Boron nitride is more effective than carbon black (also 4 vol.%) for enhancing the conductance, but carbon black diminishes the heat of fusion less than does boron nitride.     

Rheological Behavior of Thermal Interface Pastes

Polyol-ester-based thermal pastes containing carbon black, fumed alumina or nanoclay exhibit Bingham plastic behavior with shear thinning. Carbon black gives double yielding, but fumed alumina and nanoclay give single yielding. The plastic viscosity increases with the solid content. Antioxidants increase the plastic viscosity and yield stresses. Nanoclay (1.0 vol.%) gives low shear moduli, high critical shear strain, and high loss tangent, thus resulting in low bond-line thickness and high thermal contact conductance for smooth (0.009 μm) proximate surfaces. Carbon black (Tokai, 8.0 vol.%) gives high moduli, low critical strain, and low loss tangent, thus resulting in high bond-line thickness, though the high thermal conductivity due to the high solid content results in high thermal contact conductance for rough (15 μm) proximate surfaces. Antioxidants enhance the solid-like character, increase the yield stress, plastic viscosity, and bond-line thickness, and decrease the thermal contact conductance.     

Investigation of Thermal Stability and Degradation Mechanisms in Ni-Based Ohmic Contacts to <Emphasis Type="Italic">n</Emphasis>-Type SiC for High-Temperature Gas Sensors

We investigated the thermal stability of Pt/TaSi _x /Ni/SiC ohmic contacts, which have been implemented in SiC-based gas sensors developed for applications in diesel engines and power plants. The contacts remained ohmic on lightly doped n-type (~1 × 10¹⁶ cm⁻³) 4H-SiC for over 1000 h in air at 300°C. Although a gradual increase in specific contact resistance from 3.4 × 10⁻⁴ Ω cm² to 2.80 × 10⁻³ Ω cm² was observed, the values appeared to stabilize after ~800 h of heating in air at 300°C. The contacts heated at 500°C and 600°C, however, showed larger increases in specific contact resistance followed by nonohmic behavior after 240 h and 36 h, respectively. Concentration profiles from Auger electron spectroscopy and electron energy-loss spectroscopy show that loss of ohmic behavior occurs when the entire tantalum silicide layer has oxidized.     

Solid-State Electrochemical Thermal Transistors

Thermal transistors that electrically control heat flow have attracted growing attention as thermal management devices and phonon logic circuits. Although several thermal transistors are demonstrated, the use of liquid electrolytes may limit the application from the viewpoint of reliability or liquid leakage. Herein, a solid-state thermal transistor that can electrochemically control the heat flow with an on-to-off ratio of the thermal conductivity (κ) of ≈4 without using any liquid is demonstrated. The thermal transistor is a multilayer film composed of an upper electrode, strontium cobaltite (SrCoO_x), solid electrolyte, and bottom electrode. An electrochemical redox treatment at 280 °C in air repeatedly modulates the crystal structure and κ of the SrCoO_x layer. The fully oxidized perovskite-structured SrCoO₃ layer shows a high κ ≈3 .8 W m⁻¹ K⁻¹, whereas the fully reduced defect perovskite-structured SrCoO₂ layer shows a low κ ≈ 0.95 W m⁻¹ K⁻¹. The present solid-state electrochemical thermal transistor may become next-generation devices toward future thermal management technology.