Positron Studies of Bismuth Donor Centers in Silicon: Effect of Irradiation with 15 MeV Protons

Abstract:

The centers of bismuth (Bi) in silicon are being scrutinized as the defect qubits for mostly developed integrated electronics including its photonic component and we have applied the positron annihilation lifetime spectroscopy (PALS) to gain deeper insight into symmetry of the Bi impurity center whose configuration was modified by 15 MeV proton irradiation. It was revealed that hyperfine (hf) and super-hyperfine (shf) interactions of the nuclear and electron spin systems of the bismuth impurity center, ²⁰⁹Bi (J = 9/2), with the regular ²⁹Si (J = 1/2) atoms of silicon delay the essentially local event of emitting of a couple of annihilation gamma–quanta from within the crystal cell which comprises Bi impurity atom (J is the nuclear spin). This phenomenon is observed under increasing occupancy of Bi donor ground and excited states, in contrast to a profoundly enriched ²⁸Si (J = 0) material (so-called “semiconductor vacuum”) where content of ²⁹Si (J = 1/2) isotope was suppressed up to the value of ≈ 50 ppm. The many-body exciton-like states comprising a polyelectronic exciton {e⁻e⁺e⁻h} at Bi donor center are suggested for interpreting the data. The proton irradiation leads to acquiring by Bi impurity atom of an open volume ( V_op ) which is splitted in [V_op – Bi] complex. This defect possessing of D_3d symmetry dominates in the irradiated material. Being thermally stable up to ≈ 370 °C, [V_op – Bi] complex is annealed at ~ 470 – 500 °C. These data agree well with the results of ab intio cluster calculations performed on the basis of LDA-KKR formalism for exploring both the energy gain and symmetry of Bi–vacancy complex.

• Periodical: Solid State Phenomena (Volume 374)
• Pages: 63-68
• DOI: https://doi.org/10.4028/p-KMUXc9
• Online since: July 2025
• Authors: Nikolai Yu. Arutyunov*, Nikolay V. Abrosimov, Mohamed Elsayed, Reinhard Krause-Rehberg, Vadim V. Emtsev, Gagik A. Oganesyan, Vitalii V. Kozlovski
• Keywords: Excitons, Germanium, Group V Impurity Centers, Point Radiation Defects, Polyelectrons, Positron Annihilation, Qubits, Silicon

References

[1] B. Wilson, A. Miloshevski, D. Hooper and N. Peters, Radiation-Induced Dark Counts for Silicon Single-Photon Detectors in Space, Phys. Rev. Appl. 16 (2021) 064049–064061.

DOI: 10.1103/physrevapplied.16.064049

[2] J. Logan, K. Woller, P. Webster, C. Morath, M. Short, Open volume defect accumulation with irradiation in GaN, GaP, InAs, InP, Si, ZnO, and MgO, J. Appl. Phys. 134 (2023) 225701–225725.

DOI: 10.1063/5.0147324

[3] T. Sekiguchi, M. Steger, K. Saeedi, M. L. W. Thewalt, H. Riemann, N. V. Abrosimov and N. Nötzel, Hyperfine structure and nuclear hyperpolarization observed in the bound exciton luminescence of Bi donors in natural Si, Phys. Rev. Lett. 104 (2010)137402–137406.

DOI: 10.1103/physrevlett.104.137402

[4] H. Riemann, N. Abrosimov, N. Nötzel, Doping of silicon crystals with Bi and other volatile elements by the pedestal growth technique, ECS Trans., 3 (2006) 53–55.

DOI: 10.1149/1.2355745

[5] P. Becker, H.-J. Pohl, H. Riemann, N. Abrosimov, Enrichment of silicon for a better kilogram, Phys. Stat. Sol. A, 207 (2010) 49–66.

DOI: 10.1002/pssa.200925148

[6] V. V. Emtsev, A. M. Ivanov, V. V. Kozlovski, A. A. Lebedev, G. A. Oganesyan, N .B. Strokan, G. Wagner, Similarities and distinctions of defect production by fast electron and proton irradiation: moderatly doped silicon and silicon carbide of n-type, Fiz. Tekh. Poluprov. 46 (2012) 473–481.

DOI: 10.1134/s1063782612040069

[7] N. Yu. Arutyunov, M. Elsayed, R. Krause-Rehberg, V.V. Emtsev, G.A. Oganesyan, V.V. Kozlovski, Positron annihilation on defects in silicon irradiated with 15 MeV protons, J. Phys.: Condens. Matter 25 (2013) 035801–035828.

DOI: 10.1088/0953-8984/25/3/035801

[8] E. Boronski, R. Nieminen, Electron-positron density-functional theory, Phys. Rev.B 34 (1986) 3820 –3831.

DOI: 10.1103/physrevb.34.3820

[9] J. Li, N. H. Le, K. L. Litvinenko, et al., Radii of Rydberg states of isolated silicon donors, Phys. Rev. B 98 (2018) 085423-1–085431-8.

[10] C. Bussolati, A. Dupasquier, L. Zappa, Positron bound states in alkali halides, Nuovo Cimento B 52 (1967) 529–538.

DOI: 10.1007/bf02711095

[11] L. Simons, The Existence of Positronium Chloride, Phys. Rev. 90 (1953) 165–166.

DOI: 10.1103/physrev.90.165

[12] G. Wolfowicz, A. M. Tyryshkin, R. E. George, H. Riemann, N. V. Abrosimov, P. Becker, H.-J. Pohl, M. L. W. Thewalt, S. A. Lyon, J. J. L. Morton, Atomic clock transitions in silicon-based spin qubits, Nature Nanotechnology 8 (2013)561–564.

DOI: 10.1038/nnano.2013.117

[13] N. Arutyunov, R. Krause-Rehberg, M. Elsayed, V. Emtsev, N. Abrosimov, G. Oganesyan, V. Kozlovski, Microstructure of bismuth centers in silicon before and after irradiation with 15 MeV protons, J. Phys. Condens.Matter 33 (2021) 245702–245717.

DOI: 10.1088/1361-648x/abe96f

[14] H. Höhler, N. Atodiresei, K. Schroeder, R. Zeller, P. H. Dederichs, Vacancy complexes with oversized impurities in Si and Ge, Phys. Rev. B 71 (2005) 035212–035219.

DOI: 10.1103/physrevb.71.035212

[15] D. V. Makhov, L. J. Lewis, Stable fourfold configurations for small vacancy clusters in silicon from ab initio calculations, Phys. Rev. Lett. 92 (2004) 255504–255508.

DOI: 10.1103/physrevlett.92.255504

[16] T. E. M. Staab, A. Sieck, M. Haugk, M. J. Puska, Th. Frauenheim, H. S. Leipner, Stability of large vacancy clusters in silicon, Phys. Rev. B 65 (2002)115210–115221.

DOI: 10.1103/physrevb.65.115210

[17] G. D. Watkins, Defects in irradiated silicon: EPR of the tin-vacancy pair, Phys. Rev.B 12 (1975) 4383-4390.

DOI: 10.1103/physrevb.12.4383

[18] S. Bubin, L. Adamowicz, Nonrelativistic variational calculations of the positronium molecule and the positronium hydride, Phys. Rev. A 74 (2006) 052502-1–052502-5.

DOI: 10.1103/physreva.74.052502