journal article·2025-09-01Open access

Optical properties of intrinsic vacancy and interstitial defects in AlN

Lei Zhu, Xingfan Zhang, You Lu, Thomas W. Keal, John Buckeridge, C. Richard A. Catlow, Alexey A. Sokol

APL Materials· Volume 13· Issue 9

Abstract

Aluminum nitride (AlN), a wide-band-gap semiconductor, is a key material for ultraviolet optoelectronics and emerging quantum technologies. However, its performance is significantly affected by intrinsic point defects that introduce deep and shallow levels within the bandgap. Here, we combine a hybrid quantum mechanical/molecular mechanical embedded cluster approach with direct comparison to photoluminescence and cathodoluminescence measurements to investigate the optical transition properties of the four most stable intrinsic point defects in AlN: aluminum vacancies, nitrogen vacancies, aluminum interstitials, and nitrogen interstitials. Calculated configuration-coordinate diagrams across all relevant charge states enable the assignment of experimentally observed optical bands to specific defect-related transitions. Our results highlight N vacancies as the dominant contributors to optical signals under most growth conditions. Although we find that Al vacancies are frequently associated with blue-to-UV optical transitions, their actual contribution remains uncertain due to the dependence of their formation on donor-rich environments. N split-interstitials also play a significant role depending on concentrations and growth conditions. This theoretical analysis, grounded firmly in suitable experimental compaisons, advances the understanding of defect-related optical properties in AlN and offers guidance for the design of optoelectronic and quantum devices.
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Research context

OpenAlex topics: GaN-based semiconductor devices and materials · Acoustic Wave Resonator Technologies · Ga2O3 and related materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, University College London 1 , 20 Gordon St., London WC1 HOAJ,

Department of Materials, University of Oxford 2 , Park Road, Oxford OX1 3PH,

STFC Scientific Computing, Daresbury Laboratory 3 , Keckwick Lane, Daresbury WA4 4AD,

School of Engineering and Design, London South Bank University 4 , 103 Borough Road, London SE1 0AA,

Energy, Materials and Environment Research Centre, London South Bank University 5 , 103 Borough Road, London SE1 0AA,

School of Chemistry, Cardiff University 6 , Main Building, Park Place, Cardiff CF10 3AT,

Funding

Engineering and Physical Sciences Research Council

References (66)

Show source-provided references
1. Aluminum nitride-an alternative ceramic substrate for high power applications in microcircuits10.1109/tchmt.1984.1136380 ↗
2. An aluminium nitride light-emitting diode with a wavelength of 210 nanometres10.1038/nature04760 ↗
3. Deep-ultraviolet light-emitting diodes with external quantum efficiency higher than 20% at 275 nm achieved by improving light-extraction efficiency10.7567/apex.10.031002 ↗
4. The emergence and prospects of deep-ultraviolet light-emitting diode technologies10.1038/s41566-019-0359-9 ↗
5. Ultraviolet semiconductor laser diodes on bulk AlN10.1063/1.2747546 ↗
6. Overview of band-edge and defect related luminescence in aluminum nitride10.1016/j.jlumin.2016.05.055 ↗
7. Single-photon emission from point defects in aluminum nitride films10.1021/acs.jpclett.0c00511 ↗
8. Quantum computing with defects10.1073/pnas.1003052107 ↗
9. The origin of 2.78 eV emission and yellow coloration in bulk AlN substrates10.1063/1.3276567 ↗
10. Strong orange luminescence from AlN whiskers10.1016/j.matlet.2012.12.042 ↗
11. Time-resolved photoluminescence characterization of 2 eV band in AlN10.1002/pssc.201400175 ↗
12. Luminescence studies of oxygen-related defects in aluminum nitride10.1111/j.1151-2916.1990.tb06444.x ↗
13. Ultraviolet luminescence in AlN10.1002/pssb.201046616 ↗
14. Influence of high-temperature processing on the surface properties of bulk AlN substrates10.1016/j.jcrysgro.2016.04.030 ↗
15. Analysis of point defects in AlN epilayers by cathodoluminescence spectroscopy10.1063/1.3154518 ↗
16. Electron paramagnetic resonance of a donor in aluminum nitride crystals10.1063/1.2173237 ↗
17. F-type centers in neutron-irradiated AIN10.1143/jjap.29.150 ↗
18. Point-defect nature of the ultraviolet absorption band in AlN10.1103/physrevapplied.9.054036 ↗
19. Characterization of bulk AlN with low oxygen content10.1016/j.jcrysgro.2004.05.071 ↗
20. Nitrogen vacancy type defect luminescence of AlN nanopowder10.1016/j.optmat.2020.110069 ↗
21. Optical properties of the nitrogen vacancy in AlN epilayers10.1063/1.1648137 ↗
22. Native defects in wurtzite GaN and AlN10.1557/proc-339-693 ↗
23. Ab initio study of oxygen point defects in GaAs, GaN, and AlN10.1103/physrevb.54.16676 ↗
24. Calculated defect levels in GaN and AlN and their pressure coefficients10.1016/s0038-1098(96)00689-8 ↗
25. Theory of point defects in GaN, AlN, and BN: Relaxation and pressure effects10.1103/physrevb.60.8147 ↗
26. Theoretical evidence for the semi-insulating character of AlN10.1063/1.369197 ↗
27. Theoretical investigation of native defects, impurities, and complexes in aluminum nitride10.1103/physrevb.65.155212 ↗
28. Design of defect spins in piezoelectric aluminum nitride for solid-state hybrid quantum technologies10.1038/srep20803 ↗
29. Native and radiation induced point defects in AlN and Sc-doped AlN10.1103/physrevmaterials.6.094603 ↗
30. Native defect properties and p-type doping efficiency in group-IIA doped wurtzite AlN10.1103/PhysRevB.77.035201 ↗
31. Hybrid functional investigations of band gaps and band alignments for AlN, GaN, InN, and InGaN10.1063/1.3548872 ↗
32. Hybrid functional study of Si and O donors in wurtzite AlN10.1063/1.3641861 ↗
33. Hybrid functional calculations of DX centers in AlN and GaN10.1103/PhysRevB.89.085204 ↗
34. Origins of optical absorption and emission lines in AlN10.1063/1.4895786 ↗
35. Characterization of the nitrogen split interstitial defect in wurtzite aluminum nitride using density functional theory10.1063/1.4895843 ↗
36. Defects in AlN as candidates for solid-state qubits10.1103/physrevb.93.161201 ↗
37. On compensation in Si-doped AlN10.1063/1.5022794 ↗
38. Point defects in group III nitrides: A comparative first-principles study10.1063/1.5094356 ↗
39. Scandium-based point defect in AlN for quantum information processing10.1103/physrevb.110.125116 ↗
40. Oxygen impurities in AlN and their impact on optical absorption10.1063/5.0234655 ↗
41. Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs10.1103/physrevb.78.235104 ↗
42. Correcting the corrections for charged defects in crystals10.1038/s41524-021-00546-0 ↗
43. Effect of dielectric polarization on the properties of charged point defects in insulating crystals: The nitrogen vacancy in AlN10.1088/0953-8984/16/20/008 ↗
44. Nitrogen vacancy and oxygen impurity in AlN: Spintronic quantum dots10.1080/10420150903188443 ↗
45. Hybrid QM/MM embedding approach for the treatment of localized surface states in ionic materials10.1002/qua.20032 ↗
46. Formation of intrinsic point defects in AlN: A study of donor and acceptor characteristics using hybrid QM/MM techniques10.1039/d4ta04335a ↗
47. QUASI: A general purpose implementation of the QM/MM approach and its application to problems in catalysis10.1016/s0166-1280(03)00285-9 ↗
48. DL-FIND: An open-source geometry optimizer for atomistic simulations10.1021/jp9028968 ↗
49. Open-source, Python-based redevelopment of the ChemShell multiscale QM/MM environment10.1021/acs.jctc.8b01036 ↗
50. NWChem: Past, present, and future10.1063/5.0004997 ↗
51. Hybrid exchange-correlation functional determined from thermochemical data and ab initio potentials10.1063/1.1412605 ↗
52. Development and assessment of a new hybrid density functional model for thermochemical kinetics10.1021/jp049908s ↗
53. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy10.1039/b508541a ↗
54. The general utility lattice program (GULP)10.1080/0892702031000104887 ↗
55. GULP: A computer program for the symmetry-adapted simulation of solids10.1039/a606455h ↗
56. Computational study of native defects and defect migration in wurtzite AlN: An atomistic approach10.1039/d2ta09503c ↗
57. Rationale for mixing exact exchange with density functional approximations10.1063/1.472933 ↗
58. Toward reliable density functional methods without adjustable parameters: The PBE0 model10.1063/1.478522 ↗
59. Equilibrium point defect and charge carrier concentrations in a material determined through calculation of the self-consistent Fermi energy10.1016/j.cpc.2019.06.017 ↗
60. Ab initio molecular dynamics for liquid metals10.1103/physrevb.47.558 ↗
61. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set10.1103/PhysRevB.54.11169 ↗
62. From ultrasoft pseudopotentials to the projector augmented-wave method10.1103/physrevb.59.1758 ↗
63. Ain single crystals10.1016/0022-0248(77)90246-9 ↗
64. Ultrawide-bandgap semiconductor AlN crystals: Growth and applications10.1039/d0tc04182c ↗
65. Identification of luminescent defects in wide-bandgap semiconductors using first-principles10.1088/1361-648x/adec2d ↗
66. Shallow donors and deep-level color centers in bulk AlN crystals: EPR, ENDOR, ODMR and optical studies10.1007/s00723-013-0470-x ↗