journal article·2024-09Open access

Elementary excitations of single-photon emitters in hexagonal boron nitride

Jonathan Pelliciari, Enrique Mejia, John M. Woods, Yanhong Gu, Jiemin Li, Saroj B. Chand, Shiyu Fan, Kenji Watanabe, Takashi Taniguchi, Valentina Bisogni, Gabriele Grosso

Nature Materials· Volume 23· Issue 9

Abstract

Single-photon emitters serve as building blocks for many emerging concepts in quantum photonics. The recent identification of bright, tunable and stable emitters in hexagonal boron nitride (hBN) has opened the door to quantum platforms operating across the infrared to ultraviolet spectrum. Although it is widely acknowledged that defects are responsible for single-photon emitters in hBN, crucial details regarding their origin, electronic levels and orbital involvement remain unknown. Here we employ a combination of resonant inelastic X-ray scattering and photoluminescence spectroscopy in defective hBN, unveiling an elementary excitation at 285 meV that gives rise to a plethora of harmonics correlated with single-photon emitters. We discuss the importance of N π* anti-bonding orbitals in shaping the electronic states of the emitters. The discovery of elementary excitations in hBN provides fundamental insights into quantum emission in low-dimensional materials, paving the way for future investigations in other platforms.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Diamond and Carbon-based Materials Research · Boron and Carbon Nanomaterials Research · Graphene research and applications

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

References (48)

Show source-provided references
1. Caldwell, J. D. et al. Photonics with hexagonal boron nitride. Nat. Rev. Mater. 4, 552–567 (2019).10.1038/s41578-019-0124-1 ↗
2. Tran, T. T., Bray, K., Ford, M. J., Toth, M. & Aharonovich, I. Quantum emission from hexagonal boron nitride monolayers. Nat. Nanotechnol. 11, 37–41 (2016).10.1038/nnano.2015.242 ↗
3. Bourrellier, R. et al. Bright UV single photon emission at point defects in h-BN. Nano Lett. 16, 4317–4321 (2016).10.1021/acs.nanolett.6b01368 ↗
4. Grosso, G. et al. Tunable and high-purity room temperature single-photon emission from atomic defects in hexagonal boron nitride. Nat. Commun. 8, 705 (2017).10.1038/s41467-017-00810-2 ↗
5. Fournier, C. et al. Position-controlled quantum emitters with reproducible emission wavelength in hexagonal boron nitride. Nat. Commun. 12, 3779 (2021).10.1038/s41467-021-24019-6 ↗
6. Dietrich, A. et al. Observation of Fourier transform limited lines in hexagonal boron nitride. Phys. Rev. B 98, 081414 (2018).10.1103/PhysRevB.98.081414 ↗
7. Chejanovsky, N. et al. Single-spin resonance in a van der Waals embedded paramagnetic defect. Nat. Mater. 20, 1079–1084 (2021).10.1038/s41563-021-00979-4 ↗
8. Jungwirth, N. R. & Fuchs, G. D. Optical absorption and emission mechanisms of single defects in hexagonal boron nitride. Phys. Rev. Lett. 119, 057401 (2017).10.1103/PhysRevLett.119.057401 ↗
9. Abdi, M., Chou, J.-P., Gali, A. & Plenio, M. B. Color centers in hexagonal boron nitride monolayers: a group theory and ab initio analysis. ACS Photonics 5, 1967–1976 (2018).10.1021/acsphotonics.7b01442 ↗
10. Tawfik, S. A. et al. First-principles investigation of quantum emission from hBN defects. Nanoscale 9, 13575–13582 (2017).10.1039/C7NR04270A ↗
11. Mendelson, N. et al. Identifying carbon as the source of visible single-photon emission from hexagonal boron nitride. Nat. Mater. 20, 321–328 (2021).10.1038/s41563-020-00850-y ↗
12. Gottscholl, A. et al. Room temperature coherent control of spin defects in hexagonal boron nitride. Sci. Adv. 7, eabf3630 (2021).10.1126/sciadv.abf3630 ↗
13. Gottscholl, A. et al. Initialization and read-out of intrinsic spin defects in a van der Waals crystal at room temperature. Nat. Mater. 19, 540–545 (2020).10.1038/s41563-020-0619-6 ↗
14. Tran, T. T. et al. Robust multicolor single photon emission from point defects in hexagonal boron nitride. ACS Nano 10, 7331–7338 (2016).10.1021/acsnano.6b03602 ↗
15. Ament, L. J. P., van Veenendaal, M., Devereaux, T. P., Hill, J. P. & van den Brink, J. Resonant inelastic X-ray scattering studies of elementary excitations. Rev. Mod. Phys. 83, 705–767 (2011).10.1103/RevModPhys.83.705 ↗
16. Ament, L. J. P., van Veenendaal, M. & van den Brink, J. Determining the electron-phonon coupling strength from resonant inelastic X-ray scattering at transition metal L-edges. Europhys. Lett. 95, 27008 (2011).10.1209/0295-5075/95/27008 ↗
17. Gel’mukhanov, F., Odelius, M., Polyutov, S. P., Föhlisch, A. & Kimberg, V. Dynamics of resonant X-ray and Auger scattering. Rev. Mod. Phys. 93, 035001 (2021).10.1103/RevModPhys.93.035001 ↗
18. Dvorak, J., Jarrige, I., Bisogni, V., Coburn, S. & Leonhardt, W. Towards 10 meV resolution: the design of an ultrahigh resolution soft X-ray RIXS spectrometer. Rev. Sci. Instrum. 87, 115109 (2016).10.1063/1.4964847 ↗
19. Pelliciari, J. et al. Tuning spin excitations in magnetic films by confinement. Nat. Mater. 20, 188–193 (2021).10.1038/s41563-020-00878-0 ↗
20. Pelliciari, J. et al. Evolution of spin excitations from bulk to monolayer FeSe. Nat. Commun. 12, 3122 (2021).10.1038/s41467-021-23317-3 ↗
21. Dean, M. P. M. et al. Spin excitations in a single La2CuO4 layer. Nat. Mater. 11, 850–854 (2012).10.1038/nmat3409 ↗
22. McDougall, N. L., Partridge, J. G., Nicholls, R. J., Russo, S. P. & McCulloch, D. G. Influence of point defects on the near edge structure of hexagonal boron nitride. Phys. Rev. B 96, 144106 (2017).10.1103/PhysRevB.96.144106 ↗
23. Vinson, J., Jach, T., Müller, M., Unterumsberger, R. & Beckhoff, B. Resonant X-ray emission of hexagonal boron nitride. Phys. Rev. B 96, 205116 (2017).10.1103/PhysRevB.96.205116 ↗
24. McDougall, N. L., Nicholls, R. J., Partridge, J. G. & McCulloch, D. G. The near edge structure of hexagonal boron nitride. Microsc. Microanal. 20, 1053–1059 (2014).10.1017/S1431927614000737 ↗
25. Watanabe, K., Taniguchi, T. & Kanda, H. Direct-bandgap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. Nat. Mater. 3, 404–409 (2004).10.1038/nmat1134 ↗
26. Xu, Z.-Q. et al. Single photon emission from plasma treated 2D hexagonal boron nitride. Nanoscale 10, 7957–7965 (2018).10.1039/C7NR08222C ↗
27. Serrano, J. et al. Vibrational properties of hexagonal boron nitride: inelastic X-ray scattering and ab initio calculations. Phys. Rev. Lett. 98, 095503 (2007).10.1103/PhysRevLett.98.095503 ↗
28. Geondzhian, A. & Gilmore, K. Demonstration of resonant inelastic X-ray scattering as a probe of exciton-phonon coupling. Phys. Rev. B 98, 214305 (2018).10.1103/PhysRevB.98.214305 ↗
29. Geondzhian, A. & Gilmore, K. Generalization of the Franck-Condon model for phonon excitations by resonant inelastic X-ray scattering. Phys. Rev. B 101, 214307 (2020).10.1103/PhysRevB.101.214307 ↗
30. Feng, X. et al. Disparate exciton-phonon couplings for zone-center and boundary phonons in solid-state graphite. Phys. Rev. Lett. 125, 116401 (2020).10.1103/PhysRevLett.125.116401 ↗
31. Dashwood, C. et al. Probing electron-phonon interactions away from the Fermi level with resonant inelastic X-ray scattering. Phys. Rev. X 11, 041052 (2021).
32. Kjellsson, L. et al. Resonant inelastic X-ray scattering at the N2π∗ resonance: lifetime-vibrational interference, radiative electron rearrangement, and wave-function imaging. Phys. Rev. A 103, 022812 (2021).10.1103/PhysRevA.103.022812 ↗
33. Lindblad, R. et al. X-ray absorption spectrum of the N2+ molecular ion. Phys. Rev. Lett. 124, 203001 (2020).10.1103/PhysRevLett.124.203001 ↗
34. Ament, L. J., Van Veenendaal, M., Devereaux, T. P., Hill, J. P. & Van Den Brink, J. Resonant inelastic X-ray scattering studies of elementary excitations. Rev. Mod. Phys. 83, 705 (2011).10.1103/RevModPhys.83.705 ↗
35. Lee, J. et al. Charge-orbital-lattice coupling effects in the dd excitation profile of one-dimensional cuprates. Phys. Rev. B 89, 041104 (2014).10.1103/PhysRevB.89.041104 ↗
36. Martinelli, L. et al. Collective nature of orbital excitations in layered cuprates in the absence of apical oxygens. Phys. Rev. Lett. 132, 066004 (2024).10.1103/PhysRevLett.132.066004 ↗
37. Comtet, J. et al. Wide-field spectral super-resolution mapping of optically active defects in hexagonal boron nitride. Nano Lett. 19, 2516–2523 (2019).10.1021/acs.nanolett.9b00178 ↗
38. Hayee, F. et al. Revealing multiple classes of stable quantum emitters in hexagonal boron nitride with correlated optical and electron microscopy. Nat. Mater. 19, 534–539 (2020).10.1038/s41563-020-0616-9 ↗
39. Mendelson, N. et al. Engineering and tuning of quantum emitters in few-layer hexagonal boron nitride. ACS Nano 13, 3132–3140 (2019).10.1021/acsnano.8b08511 ↗
40. Camphausen, R. et al. Observation of near-infrared sub-Poissonian photon emission in hexagonal boron nitride at room temperature. APL Photonics 5, 076103 (2020).10.1063/5.0008242 ↗
41. Schell, A. W., Svedendahl, M. & Quidant, R. Quantum emitters in hexagonal boron nitride have spectrally tunable quantum efficiency. Adv. Mater. 30, 1704237 (2018).10.1002/adma.201704237 ↗
42. Grosso, G. et al. Low-temperature electron–phonon interaction of quantum emitters in hexagonal boron nitride. ACS Photonics 7, 1410–1417 (2020).10.1021/acsphotonics.9b01789 ↗
43. Mendelson, N., Doherty, M., Toth, M., Aharonovich, I. & Tran, T. T. Strain-induced modification of the optical characteristics of quantum emitters in hexagonal boron nitride. Adv. Mater. 32, 1908316 (2020).10.1002/adma.201908316 ↗
44. Nikolay, N. et al. Very large and reversible Stark-shift tuning of single emitters in layered hexagonal boron nitride. Phys. Rev. Appl. 11, 041001 (2019).10.1103/PhysRevApplied.11.041001 ↗
45. Williams, F. Donor-acceptor pairs in semiconductors. Phys. Status Solidi B 25, 493–512 (1968).10.1002/pssb.19680250202 ↗
46. Tan, Q. et al. Donor-acceptor pair quantum emitters in hexagonal boron nitride. Nano Lett. 22, 1331–1337 (2022).10.1021/acs.nanolett.1c04647 ↗
47. Laturia, A., Van de Put, M. L. & Vandenberghe, W. G. Dielectric properties of hexagonal boron nitride and transition metal dichalcogenides: from monolayer to bulk. npj 2D Mater. Appl. 2, 6 (2018).10.1038/s41699-018-0050-x ↗
48. Weston, L., Wickramaratne, D., Mackoit, M., Alkauskas, A. & Van de Walle, C. Native point defects and impurities in hexagonal boron nitride. Phys. Rev. B 97, 214104 (2018).10.1103/PhysRevB.97.214104 ↗