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DFT-Based Studies on Carbon Adsorption on the wz-GaN Surfaces and the Influence of Point Defects on the Stability of the Diamond–GaN Interfaces

MetadataDetails
Publication Date2021-10-29
JournalMaterials
AuthorsM. Sznajder, Roman Hrytsak
InstitutionsPolish Academy of Sciences, Rzeszów University
Citations1
AnalysisFull AI Review Included

This DFT-based study investigates interface engineering strategies for stable Diamond-GaN heterostructures, critical for improving thermal management in high-power GaN devices (HEMTs).

  • Core Problem Addressed: Abrupt Diamond-GaN interfaces (N-C and Ga-C types) exhibit poor energetic stability due to built-in electric fields (polarization) and uncompensated electron charge (monopole behavior).
  • Adsorption Preference: Carbon (C) adsorption is energetically favored on the N-terminated GaN surface (N-face, 000-1) over the Ga-terminated surface (Ga-face, 0001) by approximately 2 eV/atom.
  • Monolayer Formation: A flat carbon monolayer (precursor to diamond growth) is only stably formed on the N-face via the “on top” adsorption site.
  • Reconstruction Strategy: Energetic stability is significantly improved by introducing specific substitutional dopants in the topmost GaN layer to achieve charge neutrality (monopole-to-dipole transition) and reduce strain.
  • Optimal Dopants: The most energetically favorable reconstructions utilized Carbon substituting Nitrogen (CN) at the N-C interface (pattern 3N + 1CN) and Silicon substituting Gallium (SiGa) at the Ga-C interface (pattern 3Ga + 1SiGa).
  • Energy Gain: The maximum energy gain achieved through reconstruction was 0.53 eV/cell for the N-C interface type (3N + 1CN).
  • Diffusion Feasibility: The migration energy barrier for the charged SiN + VN3+ complex is low (0.3-0.9 eV), suggesting that vacancy-mediated diffusion of compensating dopants is feasible in bulk GaN crystals.
ParameterValueUnitContext
Diamond Lattice Parameter (Calculated)3.58ABulk crystal (a)
wz-GaN Lattice Parameter (Calculated)3.215ABulk crystal (a)
wz-GaN c/a Ratio (Calculated)1.6236DimensionlessBulk crystal
C Adsorption Energy (Ga-face, 1 ML)-7.713eV/atomMost stable site (T4, under Ga layer)
C Adsorption Energy (N-face, 1 ML)-6.760eV/atomOnly site enabling flat monolayer (On top)
N-C Interface Bond Length (Abrupt)1.48ARelaxed heterostructure
Ga-C Interface Bond Length (Abrupt)2.02ARelaxed heterostructure
Maximum Energy Gain (N-C Interface)0.53eV/cellReconstruction pattern 3N + 1CN
Total Pressure Change (N-C, 3N + 1CN)-3.276kBarEnergetically favorable reconstruction
Total Pressure Change (Ga-C, 3Ga + 1SiGa)0.735kBarEnergetically favorable reconstruction
SiN + VN3+ Migration Barrier (a-axis)0.30eVVacancy-mediated diffusion
SiN + VN3+ Migration Barrier (c-axis)0.93eVVacancy-mediated diffusion
Diamond Thermal Conductivity2000W/mKReference value
GaN Bandgap3.4eVReference value

The study relied on Density Functional Theory (DFT) calculations using the SIESTA code, focusing on structural relaxation, adsorption energy calculation, and defect migration barriers.

  1. DFT Setup: Generalized Gradient Approximation (GGA) was used for exchange-correlation. PBE functional was used for C and H atoms, and PBEJsJrHEG functional was applied for Ga and N atoms.
  2. Pseudopotentials and Basis Sets: Troullier-Martins pseudopotentials were employed. Basis sets included Double Zeta (DZ) for C-2s, Double Zeta Polarized (DZP) for C-2p, Triple Zeta (TZ) for Ga-4s/4p, Single Zeta (SZ) for Ga-3d, and Triple Zeta Polarized (TZP) for N-2p.
  3. Adsorption Modeling:
    • GaN slabs (8 double Ga-N layers) were modeled along the [0001] direction, passivated by pseudo-hydrogen atoms (0.75e or 1.25e).
    • A 30 A vacuum layer was used. Lateral cell sizes included 1x1, 2x2, and 3x3.
    • London dispersion interactions were included using the Grimme correction scheme (DFT-D).
    • Adsorption energy (Eads) was calculated relative to the clean surface and isolated C atom energy.
  4. Interface Modeling:
    • Abrupt N-C and Ga-C interfaces were constructed by overlaying the diamond structure onto the most stable C adsorption sites (on top) of the respective GaN surfaces.
    • The diamond part was strained to the GaN lateral unit cell.
    • Electrostatic potential (Vel) and valence electron charge density (Qval) profiles were computed to analyze electric fields and charge compensation.
  5. Defect and Reconstruction Modeling:
    • Substitutional dopants (C, Si) were introduced into the topmost GaN layer to test charge compensation patterns (e.g., 3N + 1CN).
    • Energy gain (Delta H) due to reconstruction was calculated based on the total energy difference between abrupt and reconstructed slabs, accounting for chemical potentials.
  6. Migration Barrier Calculation: The Nudged Elastic Band (NEB) method was used on a 5x5x3 wz-GaN supercell (300 atoms) to determine the energy barriers for vacancy-mediated diffusion of selected substitutional dopants (e.g., CN + VN).

The findings directly support the development and optimization of high-performance electronic and optoelectronic devices requiring superior thermal management, primarily through the GaN-on-Diamond architecture.

  • High-Power Radio Frequency (RF) Devices:
    • GaN-based High-Electron-Mobility Transistors (HEMTs) operating in the 5G/6G and tetrahertz communication bands.
    • Radar detection systems and high-power RF applications where heat dissipation is critical for reliability and lifetime.
  • Power Electronics:
    • Next-generation high-power switching devices and converters utilizing GaN, benefiting from the high thermal conductivity of the diamond substrate.
  • Optoelectronics:
    • Innovative GaN-based Light-Emitting Diodes (LEDs) designed for high current densities, requiring low thermal resistance to maintain efficiency and longevity.
  • Heterogeneous Integration Technology:
    • Informing the choice of optimal interfacial layers (e.g., C-rich or Si-rich) during heteroepitaxial diamond growth on GaN or during GaN-diamond bonding processes (SAB).
    • Guiding the intentional doping of the GaN substrate surface to create stable, charge-compensated interfaces, reducing thermal boundary resistance (TBReff).
View Original Abstract

Integration of diamond with GaN-based high-electron-mobility transistors improves thermal management, influencing the reliability, performance, and lifetime of GaN-based devices. The current GaN-on-diamond integration technology requires precise interface engineering and appropriate interfacial layers. In this respect, we performed first principles calculation on the stability of diamond-GaN interfaces in the framework of density functional theory. Initially, some stable adsorption sites of C atoms were found on the Ga- and N-terminated surfaces that enabled the creation of a flat carbon monolayer. Following this, a model of diamond-GaN heterojunction with the growth direction [111] was constructed based on carbon adsorption results on GaN{0001} surfaces. Finally, we demonstrate the ways of improving the energetic stability of diamond-GaN interfaces by means of certain reconstructions induced by substitutional dopants present in the topmost GaN substrate’s layer.

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