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Thermal Conductivity of BAs under Pressure

MetadataDetails
Publication Date2022-07-22
JournalAdvanced Electronic Materials
AuthorsSongrui Hou, Bo Sun, Fei Tian, Qingan Cai, Youming Xu
InstitutionsTsinghua University, University of Houston
Citations17
AnalysisFull AI Review Included

This study investigates the thermal transport properties of Boron Arsenide (BAs) single crystals under extreme compression, providing critical experimental validation for advanced phonon scattering theories.

  • Anomalous Pressure Independence: The thermal conductivity (Λ) of BAs was found to be constant (pressure-independent) between 0 and 30 GPa, a behavior highly unusual for nonmetallic crystals, which typically exhibit increasing Λ upon compression (e.g., MgO control sample).
  • High Ambient Conductivity: High-purity BAs samples demonstrated ambient thermal conductivity up to ~1100 W m-1 K-1, confirming its status as a super-thermal conductor.
  • Mechanism Validation: The constant Λ is attributed to a precise competition between pressure-induced changes in phonon scattering rates, validating first-principles predictions.
  • Scattering Balance: Compression stiffens the lattice, leading to two opposing effects: 1) Decreased acoustic bunching increases three-phonon (aaa) scattering rates. 2) Increased acoustic-optic frequency gap decreases four-phonon (aaoo) scattering rates.
  • Methodology: Measurements were performed using Time-Domain Thermoreflectance (TDTR) integrated with a Diamond Anvil Cell (DAC) to achieve GPa-scale pressures.
  • Defect Tolerance: Samples with lower ambient Λ (down to 350 W m-1 K-1, indicating higher defect concentration) also maintained pressure-independent thermal conductivity, suggesting the fundamental phonon dispersion mechanism dominates the pressure response regardless of moderate defect levels.
ParameterValueUnitContext
Pressure Range Tested (BAs)0 to 30GPaThermal conductivity measurements.
High-Purity BAs Λ (Sample A)~1100W m-1 K-1Ambient pressure (0 GPa).
Low-Purity BAs Λ (Sample C)~350W m-1 K-1Ambient pressure (0 GPa).
MgO Λ Change (Control)Factor of 2N/AIncrease observed upon compression to 20 GPa.
BAs Bulk Modulus142GPaMaterial stiffness comparison (MgO is 160 GPa).
BAs Crystal StructureZinc-blende (F43m)N/ASimple cubic structure.
Optic Phonon Frequency Increase~21 to 25THzEstimated increase from 0 to 30 GPa.
Required aaa Scattering Increase~50%N/AEstimated increase needed to offset decreased four-phonon scattering.
TDTR Pump Modulation Frequency~10MHzMeasurement setup parameter.
BAs Sample Thickness (DAC)7 ± 2”mPrepared for high-pressure measurement.
Al Transducer Thickness~80 to 90nmDeposited film for TDTR measurement.
Laser Spot Size (1/e2 radius)4.5 to 7”mUsed for TDTR measurements.

The pressure-dependent thermal conductivity of BAs was measured using Time-Domain Thermoreflectance (TDTR) within a Diamond Anvil Cell (DAC).

  1. Material Synthesis: Single crystal BAs was grown using Chemical Vapor Transport (CVT). Reactants (pure boron and arsenic) were sealed with iodine transport agent in a vacuum quartz tube.
  2. Growth Parameters: The tube was placed in a horizontal two-zone furnace, maintained at a high-temperature zone of ~890 °C and a low-temperature zone of ~800 °C.
  3. Sample Preparation: BAs crystals were polished to a final thickness of 7 ± 2 ”m. An Aluminum (Al) film (80-90 nm thick) was deposited onto the surface to act as the TDTR transducer layer.
  4. DAC Loading: Samples (50-80 ”m lateral dimension) were loaded into a DAC with a 300 ”m culet size. Stainless-steel gaskets (250 ”m thick, pre-indented) contained the sample.
  5. Pressure Medium: Silicone oil (Polydimethylsiloxane) was used as the hydrostatic pressure medium.
  6. Pressure Calibration: Pressure was monitored using the R1 line shift of ruby spheres loaded alongside the sample, and independently verified using the Brillouin oscillation frequency of the silicone oil.
  7. TDTR Measurement: A pump-probe laser system (783 nm wavelength) was used. The pump beam heats the Al transducer at a modulation frequency of ~10 MHz, and the probe beam monitors the resulting temperature decay via changes in reflectance.
  8. Data Interpretation: A bidirectional heat diffusion model was employed to analyze the TDTR signal, accounting for heat flow into both the BAs and the silicone oil. Pressure dependence of all input parameters (e.g., Al heat capacity, BAs volume change) was incorporated into the model.

The findings regarding BAs, a material with ultra-high thermal conductivity, are crucial for advancing thermal management in high-performance electronics and energy systems.

  • High-Power Electronics: BAs can serve as an advanced heat spreader or substrate material for GaN and SiC devices, enabling higher operating power densities (> 100 W/cm2) and improved reliability in power amplifiers and converters.
  • Semiconductor Manufacturing: Integration of BAs into microelectronic packaging to dissipate localized hot spots in CPUs, GPUs, and specialized accelerators, overcoming thermal bottlenecks that limit clock speed and performance.
  • Thermal Interface Materials (TIMs): Development of BAs-based composites or thin films for use as next-generation TIMs, offering superior heat transfer capabilities compared to traditional materials.
  • Aerospace and Defense: Applications requiring materials that maintain stable thermal properties under extreme mechanical stress or pressure, such as in high-G environments or specialized sensor systems.
  • Fundamental Materials Discovery: The experimental validation of phonon scattering theories under pressure provides a robust framework for computational materials science (DFT/PBE) to predict and engineer other novel materials with tailored thermal transport properties.
View Original Abstract

Abstract The thermal conductivity of boron arsenide (BAs) is believed to be influenced by phonon scattering selection rules due to its special phonon dispersion. Compression of BAs leads to significant changes in phonon dispersion, which allows for a test of first principles theories for how phonon dispersion affects three‐ and four‐phonon scattering rates. This study reports the thermal conductivity of BAs from 0 to 30 GPa. Thermal conductivity vs. pressure of BAs is measured by time‐domain thermoreflectance with a diamond anvil cell. In stark contrast to what is typical for nonmetallic crystals, BAs is observed to have a pressure independent thermal conductivity below 30 GPa. The thermal conductivity of nonmetallic crystals typically increases upon compression. The unusual pressure independence of BAs’s thermal conductivity shows the important relationship between phonon dispersion properties and three‐ and four‐phonon scattering rates.

  1. 2005 - Introduction to Solid State Physics