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Electronic structure and spin-to-charge conversion in the chalcopyrite CdGeAs2

N. Tarakameh Samani1,2,*, F. Scali1,*, C. Zucchetti1, N. Mignani1, F. Mazzola3, I. Vobornik4, J. Fujii4, K. Raju5,6, S. Mani5,6 et al.

R. Sankar5,6, M. Puppin7,8, F. Ciccacci1, M. Finazzi1, E. Carpene2, C. Dallera1, F. Bottegoni1, and A. Crepaldi1,2,†

  • *These authors contributed equally to this work.
  • †Contact author: alberto.crepaldi@polimi.it
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Phys. Rev. Materials 10, 054604 – Published 21 May, 2026

DOI: https://doi.org/10.1103/172k-l5gq

Abstract

Ternary semiconductors with chalcopyrite structure are of growing interest for electronic, energy-conversion, and spintronic applications. Using angle-resolved photoemission spectroscopy, we directly map the band structure of CdGeAs2, the prototypical chalcopyrite described by a modified Kane model that predicts the coexistence of flat bands and highly dispersive linear states. The combined effect of tetragonal distortion and broken inversion symmetry reduces the band degeneracy, allowing us to resolve three distinct states at the top of the valence band, with band velocities comparable to those reported in Dirac semimetals. We further probe the spin-to-charge conversion properties of CdGeAs2 by optically injecting spin-polarized carriers and detecting the resulting inverse spin Hall effect (ISHE). The photon-energy dependence of the ISHE signal and theoretical calculations of the optically injected spin polarization allow us to identify the specific valence-to-conduction transitions responsible for net spin accumulation and to estimate the spin diffusion length. These results demonstrate that chalcopyrite semiconductors provide a versatile platform for optospintronics.

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References (57)

  1. M. L. Cohen and J. R. Chelikowsky, Electronic Structure and Optical Properties of Semiconductors (Springer-Verlag, Berlin, 1989).
  2. W. Feng, D. Xiao, J. Ding, and Y. Yao, Three-dimensional topological insulators in I−III−VI2 and II−IV−V2 chalcopyrite semiconductors, Phys. Rev. Lett. 106, 016402 (2011).
  3. V. L. Shaposhnikov, A. V. Krivosheeva, V. E. Borisenko, J.-L. Lazzari, and F. A. d'Avitaya, Ab initio modeling of the structural, electronic, and optical properties of AIIBIVC2V semiconductors, Phys. Rev. B 85, 205201 (2012).
  4. D. Parker and D. J. Singh, Thermoelectric properties of AgGaTe2 and related chalcopyrite structure materials, Phys. Rev. B 85, 125209 (2012).
  5. J. Ruan, S.-K. Jian, D. Zhang, H. Yao, H. Zhang, S.-C. Zhang, and D. Xing, Ideal weyl semimetals in the chalcopyrites CuTlSe2, AgTlTe2, AuTlTe2, and ZnPbAs2, Phys. Rev. Lett. 116, 226801 (2016).
  6. A. Chirilá, P. Reinhard, F. Pianezzi, P. Bloesch, A. R. Uhl, C. Fella, L. Kranz, D. Keller, C. Gretener, H. Hagendorfer, et al., Potassium-induced surface modification of Cu(In,Ga)Se2 thin films for high-efficiency solar cells, Nat. Mater. 12, 1107 (2013).
  7. S. Siebentritt, Chalcopyrite compound semiconductors for thin film solar cells, Curr. Opin. Green Sustainable Chem. 4, 1 (2017).
  8. B. Sadhukhan, Y. Zhang, R. Ray, and J. van den Brink, First-principles calculation of shift current in chalcopyrite semiconductor ZnSnP2, Phys. Rev. Mater. 4, 064602 (2020).
  9. M. Rudysh, M. Piasecki, G. Myronchuk, P. Shchepanskyi, V. Stadnyk, O. Onufriv, and M. Brik, AgGaTe2—The thermoelectric and solar cell material: Structure, electronic, optical, elastic and vibrational features, Infrared Phys. Technol. 111, 103476 (2020).
  10. P. Zürcher and F. Meier, Spin-polarized photoelectrons from semiconductors with chalcopyrite structure: ZnSiAs2 and ZnGeAs2, J. Appl. Phys. 50, 3687 (1979).
  11. E. O. Kane, Band structure of indium antimonide, J. Phys. Chem. Solids. 1, 249 (1957).
  12. H. Kildal, Band structure of CdGeAs2 near k⃗=0, Phys. Rev. B 10, 5082 (1974).
  13. M. Orlita, D. M. Basko, M. S. Zholudev, F. Teppe, W. Knap, V. I. Gavrilenko, N. N. Mikhailov, S. A. Dvoretskii, P. Neugebauer, C. Faugeras, et al., Observation of three-dimensional massless Kane fermions in a zinc-blende crystal, Nat. Phys. 10, 233 (2014).
  14. A. Akrap, M. Hakl, S. Tchoumakov, I. Crassee, J. Kuba, M. O. Goerbig, C. C. Homes, O. Caha, J. Novák, F. Teppe, et al., Magneto-optical signature of massless kane electrons in Cd3As2, Phys. Rev. Lett. 117, 136401 (2016).
  15. R. Juneja, R. Shinde, and A. K. Singh, Pressure-induced topological phase transitions in CdGeSb2 and CdSnSb2, J. Phys. Chem. Lett. 9, 2202 (2018).
  16. G. G. G. V. G. Dmitriev and D. N.Nikogosyan, Handbook of Nonlinear Optical Crystals (Springer-Verlag, Berlin, 1997), pp. 176–344.
  17. V. Voelïček, Optical absorption edge of CdAs2-based glasses, Phys. Status Solidi B 67, 731 (1975).
  18. D. S. Chemla, R. F. Begley, and R. I. Byer, Experimental and theoretical studies of third-harmonic generation in the chalcopyrite CdGeAs2, IEEE J. Quantum Electron. 10, 71 (1974).
  19. S. N. Rashkeev, S. Limpijumnong, and Walter  R. L. Lambrecht, Second-harmonic generation and birefringence of some ternary pnictide semiconductors, Phys. Rev. B 59, 2737 (1999).
  20. K. L. Vodopyanov and P. G. Schunemann, Efficient difference-frequency generation of 7–20−µm radiation in CdGeAs2, Opt. Lett. 23, 1096 (1998).
  21. F. P. Baumgartner, M. Lux-Steiner, and E. Bucher, Growth of CdGeAs2 single crystals by the chemical vapor transport method, J. Electron. Mater. 19, 777 (1990).
  22. S. F. Marenkin, V. M. Novotortsev, K. K. Palkina, S. G. Mikhailov, and V. T. Kalinnikov, Preparation and structure of CdGeAs2 crystals, Inorg. Mater. 40, 93 (2004).
  23. G. Lampel, Nuclear dynamic polarization by optical electronic saturation and optical pumping in semiconductors, Phys. Rev. Lett. 20, 491 (1968).
  24. I. Žutić, J. Fabian, and S. Das Sarma, Spintronics: Fundamentals and applications, Rev. Mod. Phys. 76, 323 (2004).
  25. F. Bottegoni, C. Zucchetti, G. Isella, M. Bollani, M. Finazzi, and F. Ciccacci, Spin-charge interconversion in heterostructures based on group-IV semiconductors, Riv. Nuovo Cim. 43, 45 (2020).
  26. E. Saitoh, M. Ueda, H. Miyajima, and G. Tatara, Conversion of spin current into charge current at room temperature: Inverse spin-Hall effect, Appl. Phys. Lett. 88, 182509 (2006).
  27. C. Zucchetti, F. Bottegoni, G. Isella, M. Finazzi, F. Rortais, C. Vergnaud, J. Widiez, M. Jamet, and F. Ciccacci, Spin-to-charge conversion for hot photoexcited electrons in germanium, Phys. Rev. B 97, 125203 (2018).
  28. A. Marchionni, C. Zucchetti, F. Ciccacci, M. Finazzi, H. S. Funk, D. Schwarz, M. Oehme, J. Schulze, and F. Bottegoni, Inverse spin-Hall effect in GeSn, Appl. Phys. Lett. 118, 212402 (2021).
  29. M. Yu, X. Xiao, Z. Xiong, J. Li, X. Liu, W. Huang, B. Chen, and Z. He, Structural, electronic and optical properties of CdGeAs2 with hybrid density functional (HSE06), Mater. Today Commun. 31, 103276 (2022).
  30. M. G. Vergniory, L. Elcoro, C. Felser, B. A. B. N. Regnault, and Z. Wang, A complete catalogue of high-quality topological materials, Nature (London) 566, 480 (2019).
  31. S. Limpijumnong and Walter R. L. Lambrecht, Band structure of CdGeAs2 near the fundamental gap, Phys. Rev. B 65, 165204 (2002).
  32. T. Weber, R. Georgii, and P. Böni, Takin: An open-source software for experiment planning, visualisation, and data analysis, SoftwareX 5, 121 (2016).
  33. A. Bostwick, T. Ohta, T. Seyller, K. Horn, and E. Rotenberg, Quasiparticle dynamics in graphene, Nat. Phys. 3, 36 (2007).
  34. Z. K. Liu, J. Jiang, B. Zhou, Z. J.Wang, Y. Zhang, H. M.Weng, D. Prabhakaran, S.-K. Mo, P. D. H. Peng an, T. Kim, et al., A stable three-dimensional topological Dirac semimetal Cd3As2, Nat. Mater. 13, 677 (2014).
  35. S. Roth, H. Lee, A. Sterzi, M. Zacchigna, A. Politano, R. Sankar, F. C. Chou, G. Di Santo, L. Petaccia, O. V. Yazyev, et al., Reinvestigating the surface and bulk electronic properties of Cd3As2, Phys. Rev. B 97, 165439 (2018).
  36. Z. K. Liu, B. Zhou, Y. Zhang, Z. J. Wang, H. M. Weng, D. Prabhakaran, S.-K. Mo, Z. X. Shen, Z. Fang, X. Dai, et al., Discovery of a three-dimensional topological dirac semimetal, Na3Bi, Science 343, 864 (2014).
  37. Q. Li, D. E. Kharzeev, C. Zhang, Y. Huang, I. Pletikosic, A. V. Fedorov, R. D. Zhong, J. A. Schneeloch, G. D. Gu, and T. Valla, Chiral magnetic effect in ZrTe5, Nat. Phys. 12, 550 (2016).
  38. G. Manzoni, A. Sterzi, A. Crepaldi, M. Diego, F. Cilento, M. Zacchigna, P. Bugnon, H. Berger, A. Magrez, M. Grioni, et al., Ultrafast optical control of the electronic properties of ZrTe5, Phys. Rev. Lett. 115, 207402 (2015).
  39. S. Xue, J. Ning, B. Zhang, Q. Wu, F. Zhang, and W. Zhang, The electronic structure and optical properties of CdGeAs2 crystal: A DFT and HSE06 study, Coatings 12, 1778 (2022).
  40. F. Nastos, J. Rioux, M. Strimas-Mackey, B. S. Mendoza, and J. E. Sipe, Full band structure LDA and k·p calculations of optical spin-injection, Phys. Rev. B 76, 205113 (2007).
  41. J. Rioux and J. E. Sipe, Optical injection and control in germanium: Thirty-band k·p theory, Phys. Rev. B 81, 155215 (2010).
  42. F. Scali, M. Finazzi, F. Bottegoni, and C. Zucchetti, Optically induced orbital polarization in bulk germanium, Phys. Rev. Res. (2026).
  43. J. L. Cheng, J. Rioux, J. Fabian, and J. E. Sipe, Theory of optical spin orientation in silicon, Phys. Rev. B 83, 165211 (2011).
  44. N. Okamoto, H. Kurebayashi, T. Trypiniotis, I. Farrer, D. Ritchie, E. Saitoh, J. Sinova, J. Mašek, T. Jungwirth, and C. Barnes, Electric control of the spin Hall effect by intervalley transitions, Nat. Mater. 13, 932 (2014).
  45. D. J. Hilton and C. L. Tang, Optical orientation and femtosecond relaxation of spin-polarized holes in GaAs, Phys. Rev. Lett. 89, 146601 (2002).
  46. F. Bottegoni, C. Zucchetti, G. Isella, E. Pinotti, M. Finazzi, and F. Ciccacci, Modeling the photo-induced inverse spin-Hall effect in Pt/semiconductor junctions, J. Appl. Phys. 124, 033902 (2018).
  47. F. Scali, M. Finazzi, F. Bottegoni, and C. Zucchetti, Frequency response of spin drift-diffusion in n-doped Ge, Si, and GaAs, J. Appl. Phys. 137, 063906 (2025).
  48. C. Zucchetti, F. Bottegoni, C. Vergnaud, F. Ciccacci, G. Isella, L. Ghirardini, M. Celebrano, F. Rortais, A. Ferrari, A. Marty, et al., Imaging spin diffusion in germanium at room temperature, Phys. Rev. B 96, 014403 (2017).
  49. C. Zucchetti, F. Scali, P. Grassi, M. Bollani, L. Anzi, G. Isella, M. Finazzi, F. Ciccacci, and F. Bottegoni, Non-local architecture for spin current manipulation in silicon platforms, APL Mater. 11, 021102 (2023).
  50. C. Zucchetti, F. Scali, A. Ballabio, M. Bollani, G. Isella, G. Ferrari, M. Finazzi, F. Ciccacci, and F. Bottegoni, Hole and electron spin lifetime in lightly n-doped silicon at low temperatures, Appl. Phys. Lett. 125, 172404 (2024).
  51. G. Pikus and A. Titkov, Spin relaxation under optical orientation in semiconductors, in Modern Problems in Condensed Matter Sciences, Vol. 8 (Elsevier, New York, 1984), pp. 73–75.
  52. J. Sinova, S. O. Valenzuela, J. Wunderlich, C. H. Back, and T. Jungwirth, Spin Hall effects, Rev. Mod. Phys. 87, 1213 (2015).
  53. https://doi.org/10.5281/zenodo.19890690.
  54. D. Rideau, M. Feraille, L. Ciampolini, M. Minondo, C. Tavernier, H. Jaouen, and A. Ghetti, Strained Si, Ge, and Si1−xGex alloys modeled with a first-principles-optimized full-zone k·p method, Phys. Rev. B 74, 195208 (2006).
  55. P. Mudi, S. K. Khamari, S. Khan, C. Zucchetti, F. Bottegoni, and T. Sharma, Full-zone optical spin injection in AlxGa1−xAs alloys, J. Phys. D: Appl. Phys. 58, 015108 (2025).
  56. H. Jeschke, “Computational methods in solid state theory”, Lecture, Institut für Theoretische Physik, Goethe-Universität Frankfurt, 2016.
  57. W. Setyawan and S. Curtarolo, High-throughput electronic band structure calculations: Challenges and tools, Comput. Mater. Sci. 49, 299 (2010).

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Phys. Rev. Materials 10, 054604– Published 21 May, 2026
  • Received 3 November 2025
  • Accepted 26 March 2026
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