- Open Access
Electrically and optically active charge carrier traps in silicon-doped few-layer GaSe
Phys. Rev. Applied 26, 034034 – Published 16 September, 2026
DOI: https://doi.org/10.1103/8w6z-vwvm
Abstract
Understanding defects in atomically thin van der Waals (vdW) semiconductors is essential for advancing their use in next-generation optoelectronic and photovoltaic devices. Here, we apply a combination of various impedance spectroscopy techniques to two-dimensional (2D) vdW GaSe doped with silicon (Si) to reconstruct deep trap states across the full bandgap. Deep-level transient spectroscopy reveals three distinct deep states, 0.33, 0.68, and 0.24 eV, below the conduction band edge. Complementary deep-level optical spectroscopy and photocapacitance measurements identify two deep states at 1.4 and 1.8 eV below the conduction band edge and one at 2.0 eV above the valence band edge, with thermal admittance spectroscopy providing additional verification and further resolving two trap states at 0.16 eV above the valence band edge and at 0.26 eV below the conduction band edge. By comparing the experimentally extracted ionization energies with the predictions of density functional theory, our results attribute these trap states primarily to Si-related defects and metal vacancies. This work presents a comprehensive defect map of Si-doped GaSe, providing critical insights into carrier trapping mechanisms that are essential for optimizing the design of 2D material-based devices for industrial applications.
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References (73)
- J. Hong, C. Jin, J. Yuan, and Z. Zhang, Atomic defects in two-dimensional materials: From single-atom spectroscopy to functionalities in opto-/electronics, nanomagnetism, and catalysis, Adv. Mater. 29, 1606434 (2017).
- J. Xiong, J. Di, J. Xia, W. Zhu, and H. Li, Surface defect engineering in 2d nanomaterials for photocatalysis, Adv. Funct. Mater. 28, 1801983 (2018).
- X. Liu and M. C. Hersam, 2D materials for quantum information science, Nat. Rev. Mater. 4, 669 (2019).
- A. Carbone, D.-P. Bendixen-Fernex de Mongex, A. V. Krasheninnikov, M. Wubs, A. Huck, T. W. Hansen, A. W. Holleitner, N. Stenger, and C. Kastl, Creation and microscopic origins of single-photon emitters in transition-metal dichalcogenides and hexagonal boron nitride, Appl. Phys. Rev. 12, 031333 (2025).
- H. Cai, Y. Gu, Y.-C. Lin, Y. Yu, D. B. Geohegan, and K. Xiao, Synthesis and emerging properties of 2D layered III–VI metal chalcogenides, Appl. Phys. Rev. 6, 041312 (2019).
- M. Yu, M. Hilse, Q. Zhang, Y. Liu, Z. Wang, and S. Law, Review of nanolayered post-transition metal monochalcogenides: Synthesis, properties, and applications, ACS Appl. Nano Mater. 7, 28008 (2024).
- Z. Wang, M. Safdar, M. Mirza, K. Xu, Q. Wang, Y. Huang, F. Wang, X. Zhan, and J. He, High-performance flexible photodetectors based on nanosheets, Nanoscale 7, 7252 (2015).
- S. Sorifi, M. Moun, S. Kaushik, and R. Singh, High-temperature performance of a nanosheet-based broadband photodetector, ACS Appl. Electron. Mater. 2, 670 (2020).
- E. G. Demissie and C.-K. Siu, Theoretical understanding of the structure–property relationship of oxygen-doped gallium selenide as an efficient photocatalyst for oxygen evolution reaction, J. Phys. Chem. C 128, 10397 (2024).
- M.-W. Chen, H. K. Kim, D. Ovchinnikov, A. Kuc, T. Heine, O. Renault, and A. Kis, Large-grain MBE-grown on with a Mexican hat-like valence band dispersion, npj 2D Mater. Appl. 2, 2 (2018).
- A. Budweg, D. Yadav, A. Grupp, A. Leitenstorfer, M. Trushin, F. Pauly, and D. Brida, Control of excitonic absorption by thickness variation in few-layer , Phys. Rev. B 100, 045404 (2019).
- D. V. Rybkovskiy, A. V. Osadchy, and E. D. Obraztsova, Transition from parabolic to ring-shaped valence band maximum in few-layer gas, , and , Phys. Rev. B 90, 235302 (2014).
- T. Cao, Z. Li, and S. G. Louie, Tunable magnetism and half-metallicity in hole-doped monolayer , Phys. Rev. Lett. 114, 236602 (2015).
- D. Wickramaratne, F. Zahid, and R. K. Lake, Electronic and thermoelectric properties of van der Waals materials with ring-shaped valence bands, J. Appl. Phys. 118, 075101 (2015).
- Z. Xu, Q. Xia, L. Zhang, and G. Gao, A van der Waals p–n heterostructure of : A high thermoelectric figure of merit and strong anisotropy, Nanoscale 16, 2513 (2024).
- D. Leykam, S. Flach, O. Bahat-Treidel, and A. S. Desyatnikov, Flat band states: Disorder and nonlinearity, Phys. Rev. B 88, 224203 (2013).
- P. Das, D. Wickramaratne, B. Debnath, G. Yin, and R. K. Lake, Charged impurity scattering in two-dimensional materials with ring-shaped valence bands: , , , and , Phys. Rev. B 99, 085409 (2019).
- J. H. Neave, P. J. Dobson, J. J. Harris, P. Dawson, and B. A. Joyce, Silicon doping of MBE-grown films, Appl. Phys. A 32, 195 (1983).
- M. Suezawa, A. Kasuya, Y. Nishina, and K. Sumino, Optical studies of heat-treated -doped bulk crystals, J. Appl. Phys. 69, 1618 (1991).
- C. Domke, P. Ebert, M. Heinrich, and K. Urban, Microscopic identification of the compensation mechanisms in -doped GaAs, Phys. Rev. B 54, 10288 (1996).
- D. Ruhstorfer, S. Mejia, M. Ramsteiner, M. Döblinger, H. Riedl, J. J. Finley, and G. Koblmüller, Demonstration of -type behavior in catalyst-free -doped GaAs nanowires grown by molecular beam epitaxy, Appl. Phys. Lett. 116, 052101 (2020).
- J. Klein, M. Lorke, M. Florian, F. Sigger, L. Sigl, S. Rey, J. Wierzbowski, J. Cerne, K. Müller, E. Mitterreiter, P. Zimmermann, T. Taniguchi, K. Watanabe, U. Wurstbauer, M. Kaniber, M. Knap, R. Schmidt, J. J. Finley, and A. W. Holleitner, Site-selectively generated photon emitters in monolayer via local helium ion irradiation, Nat. Commun. 10, 2755 (2019).
- L. G. Cançado, A. Jorio, E. H. M. Ferreira, F. Stavale, C. A. Achete, R. B. Capaz, M. V. O. Moutinho, A. Lombardo, T. S. Kulmala, and A. C. Ferrari, Quantifying defects in graphene via Raman spectroscopy at different excitation energies, Nano Lett. 11, 3190 (2011).
- T. Grünleitner, A. Henning, M. Bissolo, M. Zengerle, L. Gregoratti, M. Amati, P. Zeller, J. Eichhorn, A. V. Stier, A. W. Holleitner, J. J. Finley, and I. D. Sharp, Real-time investigation of sulfur vacancy generation and passivation in monolayer molybdenum disulfide via in situ X-ray photoelectron spectromicroscopy, ACS Nano 16, 20364 (2022).
- T. Ohta, A. Klust, J. A. Adams, Q. Yu, M. A. Olmstead, and F. S. Ohuchi, Atomic structures of defects at heterointerfaces studied by scanning tunneling microscopy, Phys. Rev. B 69, 125322 (2004).
- W. Zhou, X. Zou, S. Najmaei, Z. Liu, Y. Shi, J. Kong, J. Lou, P. M. Ajayan, B. I. Yakobson, and J.-C. Idrobo, Intrinsic structural defects in monolayer molybdenum disulfide, Nano Lett. 13, 2615 (2013).
- P. Ci, X. Tian, J. Kang, A. Salazar, K. Eriguchi, S. Warkander, K. Tang, J. Liu, Y. Chen, S. Tongay, W. Walukiewicz, J. Miao, O. Dubon, and J. Wu, Chemical trends of deep levels in van der Waals semiconductors, Nat. Commun. 11, 5373 (2020).
- Y. Zhao, M. Tripathi, K. Čerņevičs, A. Avsar, H. G. Ji, J. F. Gonzalez Marin, C.-Y. Cheon, Z. Wang, O. V. Yazyev, and A. Kis, Electrical spectroscopy of defect states and their hybridization in monolayer , Nat. Commun. 14, 44 (2023).
- H. Ghadi, J. F. McGlone, Z. Feng, A. F. M. A. U. Bhuiyan, H. Zhao, A. R. Arehart, and S. A. Ringel, Influence of growth temperature on defect states throughout the bandgap of MOCVD-grown , Appl. Phys. Lett. 117, 172106 (2020).
- P. Kruszewski, K. Sakowski, K. Gościński, and P. Prystawko, The photoionization processes of deep trap levels in n- films grown by MOVPE technique on ammono- substrates, Appl. Sci. 14, 8785 (2024).
- T. Knobloch, Y. Y. Illarionov, F. Ducry, C. Schleich, S. Wachter, K. Watanabe, T. Taniguchi, T. Mueller, M. Waltl, M. Lanza, M. I. Vexler, M. Luisier, and T. Grasser, The performance limits of hexagonal boron nitride as an insulator for scaled CMOS devices based on two-dimensional materials, Nat. Electron. 4, 98 (2021).
- See Supplemental Material at http://link.aps.org/supplemental/10.1103/8w6z-vwvm for additional experimental details, theoretical derivations, supporting DFT calculations, and further device characterization.
- A. Kurtz, E. Muñoz, J. M. Chauveau, and A. Hierro, Deep-level spectroscopy in metal–insulator–semiconductor structures, J. Phys. D 50, 065104 (2017).
- S. Shigetomi and T. Ikari, Impurity effect on electrical conduction in n- doped with , and , Jpn. J. Appl. Phys. 44, 7521 (2005).
- D. V. Lang, Deep-level transient spectroscopy: A new method to characterize traps in semiconductors, J. Appl. Phys. 45, 3023 (1974).
- E. Mooser and M. Schlüter, The band-gap excitons in gallium selenide, Il Nuovo Cimento B (1971-1996) 18, 164 (2008).
- G. Ottaviani, C. Canali, F. Nava, P. Schmid, E. Mooser, R. Minder, and I. Zschokke, : A layer compound with anomalous valence band anisotropy, Solid State Commun. 14, 933 (1974).
- G. Lucovsky, On the photoionization of deep impurity centers in semiconductors, Solid State Commun. 3, 299 (1965).
- N. C. Fernelius, Properties of gallium selenide single crystal, Prog. Cryst. Growth Charact. Mater. 28, 275 (1994).
- S. G. Choi, D. H. Levi, C. Martinez-Tomas, and V. Muñoz Sanjosé, Above-bandgap ordinary optical properties of single crystal, J. Appl. Phys. 106, 053517 (2009).
- A. Gaur, D. Chiappe, D. Lin, D. Cott, I. Asselberghs, M. Heyns, and I. Radu, Analysis of admittance measurements of MOS capacitors on CVD grown bilayer , 2D Mater. 6, 035035 (2019).
- S. Sze and K. K. Ng, Physics of Semiconductor Devices, 3rd ed. (John Wiley & Sons, Inc., Hoboken, 2007).
- D. K. Schroder, Semiconductor Material and Device Characterization, 3rd ed. (John Wiley & Sons, Inc., Hoboken, 2006).
- R. Schifano, E. V. Monakhov, B. G. Svensson, W. Mtangi, P. Janse van Rensburg, and F. D. Auret, Shallow levels in virgin hydrothermally grown n-type studied by thermal admittance spectroscopy, Physica B 404, 4344 (2009).
- Z. Ben Aziza, V. Zólyomi, H. Henck, D. Pierucci, M. G. Silly, J. Avila, S. J. Magorrian, J. Chaste, C. Chen, M. Yoon, K. Xiao, F. Sirotti, M. C. Asensio, E. Lhuillier, M. Eddrief, V. I. Fal’ko, and A. Ouerghi, Valence band inversion and spin-orbit effects in the electronic structure of monolayer , Phys. Rev. B 98, 115405 (2018).
- P. Hartnagel, S. Ravishankar, B. Klingebiel, O. Thimm, and T. Kirchartz, Comparing methods of characterizing energetic disorder in organic solar cells, Adv. Energy Mater. 13, 2300329 (2023).
- P. Deák, M. Han, M. Lorke, M. F. Tabriz, and T. Frauenheim, Intrinsic defects of , J. Phys. Condens. Matter 32, 285503 (2020).
- C. Manfredotti, R. Murri, A. Quirini, and L. Vasanelli, Photoelectronic properties of n-, Phys. Status Solidi 38, 685 (1976).
- V. Capozzi and A. Minafra, Photoluminescence properties of -doped , J. Phys. C 14, 4335 (1981).
- V. Capozzi, Kinetics of radiative recombinations in and influence of doping on the luminescence spectra, Phys. Rev. B 28, 4620 (1983).
- V. Capozzi and M. Montagna, Optical spectroscopy of extrinsic recombinations in gallium selenide, Phys. Rev. B 40, 3182 (1989).
- Y. Cui, R. Dupere, A. Burger, D. Johnstone, K. C. Mandal, and S. A. Payne, Acceptor levels in : In crystals investigated by deep-level transient spectroscopy and photoluminescence, J. Appl. Phys. 103, 013710 (2008).
- M. K. Anis and A. R. Piercy, Electrical conduction in p-, J. Phys. D 17, 1229 (1984).
- R. A. Redkin, N. I. Onishchenko, A. V. Kosobutsky, V. N. Brudnyi, X. Su, and S. Y. Sarkisov, Temperature-dependent optical absorption and DLTS study of as-grown and electron-irradiated crystals, Crystals 15, 372 (2025).
- G. Micocci, P. Siciliano, and A. Tepore, Deep level spectroscopy in p- single crystals, J. Appl. Phys. 67, 6581 (1990).
- D. G. Hopkinson, V. Zólyomi, A. P. Rooney, N. Clark, D. J. Terry, M. Hamer, D. J. Lewis, C. S. Allen, A. I. Kirkland, Y. Andreev, Z. Kudrynskyi, Z. Kovalyuk, A. Patanè, V. I. Fal’ko, R. Gorbachev, and S. J. Haigh, Formation and healing of defects in atomically thin and , ACS Nano 13, 5112 (2019).
- G. Micocci, A. Serra, and A. Tepore, Impurity levels in -doped semiconductor, Phys. Status Solidi 162, 649 (1997).
- S. Shigetomi and T. Ikari, Optical and electrical properties of p- doped with in, Jpn. J. Appl. Phys. 46, 5774 (2007).
- L. Shi, Q. Li, Y. Ouyang, and J. Wang, Effect of illumination and vacancies on fast oxidation of ultrathin gallium selenide, Nanoscale 10, 12180 (2018).
- P. Tonndorf, S. Schwarz, J. Kern, I. Niehues, O. Del Pozo-Zamudio, A. I. Dmitriev, A. P. Bakhtinov, D. N. Borisenko, N. N. Kolesnikov, A. I. Tartakovskii, S. Michaelis de Vasconcellos, and R. Bratschitsch, Single-photon emitters in , 2D Mater. 4, 021010 (2017).
- E. Zallo, A. Pianetti, A. S. Prikhodko, S. Cecchi, Y. S. Zaytseva, A. Giuliani, M. Kremser, N. I. Borgardt, J. J. Finley, F. Arciprete, M. Palummo, O. Pulci, and R. Calarco, Two-dimensional single crystal monoclinic gallium telluride on silicon substrate via transformation of epitaxial hexagonal phase, npj 2D Mater. Appl. 7, 19 (2023).
- M. Bissolo, M. Hanke, R. Calarco, J. J. Finley, G. Koblmüller, J. M. J. Lopes, and E. Zallo, van der Waals epitaxy of 2d gallium telluride on graphene: Growth dynamics and principal component analysis, Small 21, 2503993 (2025).
- M. Bissolo, M. Dembecki, J. Belz, J. Schabesberger, M. Bergmann, P. Avdienko, F. Rauscher, A. S. Ulhe, H. Riedl, K. Volz, J. J. Finley, E. Zallo, and G. Koblmüller, Unveiling the growth mode diagram of on sapphire, Commun. Mater. 6, 279 (2025).
- A. Pianetti, S. Cecchi, M. Hanke, J. J. Finley, F. Arciprete, R. Calarco, and E. Zallo, Epitaxy and phase stability of 2d hexagonal gallium telluride on silicon, Phys. Status Solidi RRL 20, e202500432 (2025).
- Z. Liu, J. Wang, B. Chen, Y. Wei, W. Liu, and J. Liu, Giant enhancement of continuous wave second harmonic generation from few-layer coupled to high-q quasi bound states in the continuum, Nano Lett. 21, 7405 (2021).
- C. Xue, C. Tan, X. Gao, J. Tang, W. Sun, Y. Yin, M. Wang, X. Gao, H. An, B. Fu, W. Liu, Y. Wang, Y. Li, F. Ding, and H. Peng, Wafer-scale uniform epitaxy of transferable 2d single crystals for gate-all-around nanosheet field effect transistors, Nat. Commun. 16, 10587 (2025).
- G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
- G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59, 1758 (1999).
- A. Tkatchenko and M. Scheffler, Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data, Phys. Rev. Lett. 102, 073005 (2009).
- J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
- A. V. Krukau, O. A. Vydrov, A. F. Izmaylov, and G. E. Scuseria, Influence of the exchange screening parameter on the performance of screened hybrid functionals, J. Chem. Phys. 125, 224106 (2006).
- M. Farzalipour Tabriz, B. Aradi, T. Frauenheim, and P. Deák, SLABCC: Total energy correction code for charged periodic slab models, Comput. Phys. Commun. 240, 101 (2019).
- C. Freysoldt, B. Grabowski, T. Hickel, J. Neugebauer, G. Kresse, A. Janotti, and C. G. Van de Walle, First-principles calculations for point defects in solids, Rev. Mod. Phys. 86, 253 (2014).