Natalie Segercrantz

Highly mismatched GaN1-xSbx alloys: Synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA.

Native point defects in GaSb

We have applied positron annihilation spectroscopy to study native point defects in Te-doped n-type and nominally undoped p-type GaSb single crystals. The results show that the dominant vacancy defect trapping positrons in bulk GaSb is the gallium monovacancy. The temperature dependence of the average positron lifetime in both p- and n-type GaSb indicates that negative ion type defects with no associated open volume compete with the Ga vacancies. Based on comparison with theoretical predictions, these negative ions are identified as Ga antisites. The concentrations of these negatively charged defects exceed the Ga vacancy concentrations nearly by an order of magnitude. We conclude that the Ga antisite is the native defect responsible for p-type conductivity in GaSb single crystals.

Electronic band structure of highly mismatched GaN1−xSbx alloys in a broad composition range

In this letter, we study the optical properties of GaN1−xSbx thin films. Films with an Sb fraction up to 42% were synthesized by alternating GaN-GaSb layers at a constant temperature of 325 °C. The measured optical absorption data of the films are interpreted using a modified band anticrossing model that is applicable to highly mismatched alloys such as GaN1−xSbx in the entire composition range. The presented model allows us to more accurately determine the band gap as well as the band edges over the entire composition range thereby providing means for determining the composition for, e.g., efficient spontaneous photoelectrochemical cell applications.

Point defect balance in epitaxial GaSb

Positron annihilation spectroscopy in both conventional and coincidence Doppler broadening mode is used for studying the effect of growth conditions on the point defect balance in GaSb:Bi epitaxial layers grown by molecular beam epitaxy. Positron annihilation characteristics in GaSb are also calculated using density functional theory and compared to experimental results. We conclude that while the main positron trapping defect in bulk samples is the Ga antisite, the Ga vacancy is the most prominent trap in the samples grown by molecular beam epitaxy. The results suggest that the p–type conductivity is caused by different defects in GaSb grown with different methods.

The influence of nitrogen and antimony on the optical quality of InNAs(Sb) alloys

In this work we present detailed studies of the influence of nitrogen and antimony on the optical quality of InNAs(Sb) alloys. We employed photoluminescence, photoreflectance and positron annihilation spectroscopy to reveal the role of antimony and nitrogen on the improvement/degradation of the optical qualities of InNAs(Sb) alloys. A series of 1 μm-thick InNAs(Sb) layers with different nitrogen and antimony concentrations were grown by molecular beam epitaxy. The results of these investigations show that Sb atoms serve as a surfactant which effectively improves the optical quality of InNAsSb alloys. The influence of nitrogen on the optical quality however is not the same as to what has been reported for other dilute nitrides. We observed an improvement of the optical quality for some nitrogen contents. These issues are comprehensively examined and explained.

Highly mismatched GaN1−xSbxalloys: synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA.

Increased p-type conductivity in GaNxSb1-x, experimental and theoretical aspects

The large increase in the p-type conductivity observed when nitrogen is added to GaSb has been studied using positron annihilation spectroscopy and ab initio calculations. Doppler broadening measurements have been conducted on samples of GaN x Sb 1− x layers grown by molecular beam epitaxy, and the results have been compared with calculated first-principle results corresponding to different defect structures. From the calculated data, binding energies for nitrogen-related defects have also been estimated. Based on the results, the increase in residual hole concentration is explained by an increase in the fraction of negative acceptor-type defects in the material. As the band gap decreases with increasing N concentration, the ionization levels of the defects move closer to the valence band. Ga vacancy-type defects are found to act as positron trapping defects in the material, and the ratio of Ga vacancy-type defects to Ga antisites is found to be higher than that of the p-type bulk GaSb substrate. Beside Ga vacancies, the calculated results imply that complexes of a Ga vacancy and nitrogen could be present in the material.

Intermixing studies in GaN_1−xSb_x highly mismatched alloys

GaN1-xSbx with x∼5%-7% is a highly mismatched alloy predicted to have favorable properties for application as an electrode in a photoelectrochemical cell for solar water splitting. In this study, we grew GaN1-xSbx under conditions intended to induce phase segregation. Prior experiments with the similar alloy GaN1-xAsx, the tendency of Sb to surfact, and the low growth temperatures needed to incorporate Sb all suggested that GaN1-xSbx alloys would likely exhibit phase segregation. We found that, except for very high Sb compositions, this was not the case and that instead interdiffusion dominated. Characteristics measured by optical absorption were similar to intentionally grown bulk alloys for the same composition. Furthermore, the alloys produced by this method maintained crystallinity for very high Sb compositions and allowed higher overall Sb compositions. This method may allow higher temperature growth while still achieving needed Sb compositions for solar water splitting applications.

Intermixing studies in GaN1−xSbx highly mismatched alloys

GaN1-xSbx with x∼5%-7% is a highly mismatched alloy predicted to have favorable properties for application as an electrode in a photoelectrochemical cell for solar water splitting. In this study, we grew GaN1-xSbx under conditions intended to induce phase segregation. Prior experiments with the similar alloy GaN1-xAsx, the tendency of Sb to surfact, and the low growth temperatures needed to incorporate Sb all suggested that GaN1-xSbx alloys would likely exhibit phase segregation. We found that, except for very high Sb compositions, this was not the case and that instead interdiffusion dominated. Characteristics measured by optical absorption were similar to intentionally grown bulk alloys for the same composition. Furthermore, the alloys produced by this method maintained crystallinity for very high Sb compositions and allowed higher overall Sb compositions. This method may allow higher temperature growth while still achieving needed Sb compositions for solar water splitting applications.

Intermixing studies in GaN 1−x Sb x highly mismatched alloys

GaN1-xSbx with x∼5%-7% is a highly mismatched alloy predicted to have favorable properties for application as an electrode in a photoelectrochemical cell for solar water splitting. In this study, we grew GaN1-xSbx under conditions intended to induce phase segregation. Prior experiments with the similar alloy GaN1-xAsx, the tendency of Sb to surfact, and the low growth temperatures needed to incorporate Sb all suggested that GaN1-xSbx alloys would likely exhibit phase segregation. We found that, except for very high Sb compositions, this was not the case and that instead interdiffusion dominated. Characteristics measured by optical absorption were similar to intentionally grown bulk alloys for the same composition. Furthermore, the alloys produced by this method maintained crystallinity for very high Sb compositions and allowed higher overall Sb compositions. This method may allow higher temperature growth while still achieving needed Sb compositions for solar water splitting applications.