We demonstrate high p-type conductivity and hole concentrations >1018 cm−3 in Mg-implanted GaN. The implantation was performed at room temperature and by post-implantation annealing at 1 GPa of N2 and in a temperature range of 1200–1400 °C. The high pressure thermodynamically stabilized the GaN surface without the need of a capping layer. We introduce a “diffusion budget,” related to the diffusion length, as a convenient engineering parameter for comparing samples annealed at different temperatures and for different times. Although damage recovery, as measured by XRD, was achieved at relatively low diffusion budgets, these samples did not show p-type conductivity. Further analyses showed heavy compensation by the implantation-induced defects. Higher diffusion budgets resulted in a low Mg ionization energy (∼115 meV) and almost complete Mg activation. For even higher diffusion budgets, we observed significant loss of Mg to the surface and a commensurate reduction in the hole conductivity. High compensation at low diffusion budgets and loss of Mg at high diffusion budgets present a unique challenge for shallow implants. A direct control of the formation of compensating defects arising from the implantation damage may be necessary to achieve both hole conductivity and low Mg diffusion.
Reduction in compensation in Si-doped Al-rich AlGaN is demonstrated via chemical potential control (CPC). The chemical potentials and the resulting formation energies of carbon on the nitrogen site (CN) and cation vacancy complex with Si (VIII + nSiIII) were related to growth variables through a thermodynamic supersaturation model, which quantitatively predicted the incorporation of CN and the generation of the VIII + nSiIII complex. The compensation “knee” behavior, i.e., decreasing conductivity with increasing Si incorporation beyond a certain concentration, was successfully controlled. The maximum free carrier concentration was improved by impeding the formation of VIII + nSiIII complexes under III-richer conditions, while the impurity compensation by CN was reduced by making the growth environment N-richer. The results of Hall effect measurement and photoluminescence agreed well with quantitative theoretical predictions of the CPC model. Based on the developed model, the highest conductivity of 160 Ω−1 cm−1 with free carrier concentration of 3 × 1019 cm−3 in Al0.7Ga0.3N ever reported was achieved on single crystal AlN substrates. The demonstrated predictive power of the CPC model should greatly reduce the empirical analysis or iterative experimentation that would otherwise be necessary.
We demonstrate Si-implanted AlN with high conductivity (>1 Ω−1 cm−1) and high carrier concentration (5 × 1018 cm−3). This was enabled by Si implantation into AlN with a low threading dislocation density (TDD) (<103 cm−2), a non-equilibrium damage recovery and dopant activation annealing process, and in situ suppression of self-compensation during the annealing. Low TDD and active suppression of VAl-nSiAl complexes via defect quasi Fermi level control enabled low compensation, while low-temperature, non-equilibrium annealing maintained the desired shallow donor state with an ionization energy of ∼70 meV. The realized n-type conductivity and carrier concentration are over one order of magnitude higher than that reported thus far and present a major technological breakthrough in doping of AlN.
Self-compensation in Ge- and Si-doped Al0.3Ga0.7N has been investigated in terms of the formation of III vacancy and donor-vacancy complexes. Both Ge- and Si-doped AlGaN layers showed a compensation knee behavior with impurity compensation (low doping regime), compensation plateau (medium doping regime), and self-compensation (high doping regime). A maximum free carrier concentration of 4–5 × 1019 cm−3 was obtained by Ge doping, whereas Si doping resulted in only half of that value, ∼2 × 1019 cm−3. A DFT calculation with the grand canonical thermodynamics model was developed to support the hypothesis that the difference in self-compensation arises from the difference in the formation energies of the VIII-n•donor complexes relative to their onsite configurations. The model suggested that the VIII-2•donor and VIII-3•donor complexes were responsible for self-compensation for both Ge- and Si-doped AlGaN. However, a lower free carrier concentration in Si-doped samples was due to a high VIII-3•Si concentration, resulting from a lower energy of formation of VIII-3•Si.
Record low resistivities of 10 and 30 Ω cm and room-temperature free hole concentrations as high as 3 × 1018 cm−3 were achieved in bulk doping of Mg in Al0.6Ga0.4N films grown on AlN single crystalline wafer and sapphire. The highly conductive films exhibited a low ionization energy of 50 meV and impurity band conduction. Both high Mg concentration (>2 × 1019 cm−3) and low compensation were required to achieve impurity band conduction and high p-type conductivity. The formation of VN-related compensators was actively suppressed by chemical potential control during the deposition process. This work overcomes previous limitations in p-type aluminum gallium nitride (p-AlGaN) and offers a technologically viable solution to high p-conductivity in AlGaN and AlN.
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