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Hyperdoping consists of the intentional introduction of deep‐level dopants into a semiconductor in excess of equilibrium concentrations. This causes a broadening of dopant energy levels into an intermediate band between the valence and the conduction bands. Recently, bulk Si hyperdoped with chalcogens or transition metals is demonstrated to be an appropriate intermediate‐band material for Si‐based short‐wavelength infrared photodetectors. Intermediate‐band nanowires can potentially be used instead of bulk materials to overcome the Shockley–Queisser limit and to improve efficiency in solar cells, but fundamental scientific questions in hyperdoping Si nanowires require experimental verification. The development of a method for obtaining controlled hyperdoping levels at the nanoscale concomitant with the electrical activation of dopants is, therefore, vital to understanding these issues. Here, this paper shows a complementary metal‐oxide‐semiconductor (CMOS)‐compatible technique based on nonequilibrium processing for the controlled doping of Si at the nanoscale with dopant concentrations several orders of magnitude greater than the equilibrium solid solubility. Through the nanoscale spatially controlled implantation of dopants, and a bottom‐up template‐assisted solid phase recrystallization of the nanowires with the use of millisecond‐flash lamp annealing, Se‐hyperdoped Si/SiO2 core/shell nanowires are formed that have a room‐temperature sub‐bandgap optoelectronic photoresponse when configured as a photoconductor device.

We report on the hyperdoping of silicon with selenium obtained by ion implantation followed by flash lamp annealing. It is shown that the degree of crystalline lattice recovery of the implanted layers and the Se substitutional fraction depend on the pulse duration and energy density of the flash. While the annealing at low energy densities leads to an incomplete recrystallization, annealing at high energy densities results in a decrease of the substitutional fraction of impurities. The electrical properties of the implanted layers are well-correlated with the structural properties resulting from different annealing processing.

Semiconducting nanowires (NWs) hold promises for functional nanoscale devices [1]. Although several applications have been demonstrated in the areas of electronics, photonics and sensing, the doping of NWs remains challenging. Ion implantation is a standard doping method in top-down semiconductor industry, which offers precise control over the areal dose and depth profile as well as allows for the doping of all elements of the periodic table even beyond their equilibrium solid solubility [2]. Yet its major disadvantage is the concurrent material damage. A subsequent annealing process is commonly used for the healing of implant damage and the electrical activation of dopants. This step, however, might lead to the out-diffusion of dopants and eventually the degradation of NWs because of the low thermal stability caused by the large surface–area-to-volume ratio. In this work, we report on non-equilibrium processing for controlled doping of drop-casted Si/SiO2 core/shell NWs with shallow- and deep-level dopants below and above their equilibrium solid solubility. The approach lies on the implantation of either shallow-level dopants, such as B and P, or deep-level dopants like Se followed by millisecond flash lamp annealing. In case of amorphization upon high-fluence implantation, recrystallization takes place via a bottom-up template-assisted solid phase epitaxy. Non-equilibrium Se concentrations lead to intermediate-band Si/SiO2 core/shell NWs that have room-temperature sub-band gap photoresponse when configured as a photoconductor device [3]. Alternatively, the formation of a cross-sectional p-n junction is demonstrated by co-implanting P and B in individual NWs at different depth along the NW core. [1] Peidong Yang, Ruoxue Yan, and Melissa Fardy, Nano Lett. 2010, 10, 1529–1536 [2] Michiro Sugitani, Rev. Sci. Instrum. 2014, 85, 02C315 [3] Y. Berencén, et al. Adv. Mater. Interfaces 2018, 5, 1800101

The hyperdoping of semiconductors consists of introducing dopant concentrations far above the equilibrium solubility limits. This results in a broadening of dopant energy levels into an impurity or intermediate band. We have recently demonstrated that hyperdoping bulk Si with Se shows promise for Si-based short-wavelength infrared photodetectors [1]. Lately, silicon nanowires (NWs) have gained increasing importance as building blocks for nanodevices like field-effect transistors, light emitting devices and photovoltaic cells [2, 3]. Therefore, the comparison between hyperdoping Si nanowires and bulk Si is a common issue to be examined, which comes along with the transition from a bulk material to semiconductor NWs. In this work, we report on non-equilibrium processing for controlled hyperdoping of Si/SiO2 core/shell nanowires previously synthesized by the vapor-liquid-solid method. Our approach is based on Se implantation of the upper half of NWs followed by millisecond flash lamp annealing, which allows for a bottom-up template-assisted recrystallization of the amorphized parts of the NWs via explosive solid-phase epitaxy. The Se-hyperdoped Si NWs are successfully recrystallized and accommodate Se concentrations as high as 1021 cm-3. As a proof of device concept, a single Se-hyperdoped NW-based IR photoconductor is shown. In this way, the combination of ion implantation and flash lamp annealing as a promising nanoscale hyperdoping technology is successfully established. [1] Y. Berencén, S. Prucnal, Fang Liu, I. Skorupa, R. Hübner, L. Rebohle, S. Zhou, H. Schneider, M. Helm, and W. Skorupa, “Room-temperature short-wavelength infrared Si photodetector,” Sci. Rep. 7, 43688 (2017). [2] B. Tian, T. Cohen-Karni, Q. Qing, X. Duan, P. Xie and C.M. Lieber, “Three-dimensional, flexible nanoscale field-effect transistors as localized bioprobes,” Science 329, 831 (2010). [3] T. J. Kempa, B. Tian, D.R. Kim, J. Hu, X. Zheng and C.M. Lieber, “Single and tandem axial p-i-n nanowire photovoltaic devices,” Nano Lett. 8, 3456 (2008).

Hyperdoping of silicon using ion implantation and short time annealing of chalcogen atoms and transition metals (e.g. S, Se, Te, Au and Ti) appears as a challenging and promising research topic for developing Si-based infrared photodetectors and intermediate band solar cells [i.e.1-3]. The specific physical properties, such as a near-unity broadband absorption (particularly below the Si bandgap), a large enhancement of sub-band-gap photocurrent generation, and the insulator-to-metal transition, are based on this type of doping much above the solid solubility limit of dopants in Si. We have recently been demonstrated that both, laser annealing via the liquid phase and flash lamp annealing via the solid phase can be used to process such high-dose chalcogen-implanted layers [2]. Such kind of non-equilibrium processing needs a careful adjustment of the processing parameters, especially in regard to the “thermal engineering” with processing times at or below the millisecond range, to optimize the defect engineering of this specific type of hyperdoped material. We will report on the microstructural, optical and electrical properties of this new type of silicon material as well as first applications for room-temperature extended infrared Si p-n photodiodes. [1] J. P. Mailoa, A. J. Akey, C. B. Simmons, D. Hutchinson, J. Mathews, J. T. Sullivan, D. Recht, M. T. Winkler, J. S. Williams, J. M. Warrender, P. D. Persans, M. J. Aziz, and T. Buonassisi, Nat. Commun. 5, 3011 (2014). [2] S. Zhou, F. Liu, S. Prucnal, K. Gao, M. Khalid, C. Baehtz, M. Posselt, W. Skorupa, and M. Helm, Sci. Rep. 5, 8329 (2015). [3] F. Liu, S Prucnal, R. Hübner, Ye Yuan, W Skorupa, M Helm, and S. Zhou, J.Phys.D: Appl.Phys. 49 (2016) 245104.

The development of room-temperature Si infrared photodetectors, whose range of detection lies on the traditional telecommunication wavelengths around 1300 nm and 1550 nm, is of paramount importance for optical communications, integrated photonics, sensing and medical imaging applications [1]. The typical peak photoresponse of conventional Si photodetectors is between 700 and 900 nm, which is primarily limited by the 1.12 eV-Si band gap. However, such intrinsic material limitation can be overcome by introducing transition metals or chalcogens into the Si band gap at concentrations far above those obtained at equilibrium conditions [1, 2]. This new class of hyperdoped materials with a donor impurity band has been postulated as a viable route to extend the Si photoresponse at the infrared spectral region [3]. In this work, we report on the significant room-temperature photoresponse and performance at the two primary telecommunication wavelengths as exhibited by hyperdoped Si p-n photodiodes fabricated by Se implantation followed by millisecond flash lamp annealing (FLA). The FLA approach in the millisecond range allows for a solid-phase epitaxy that has been reported to be superior to liquid-phase epitaxy induced during pulsed laser annealing [2]. The success of our devices is primarily based on the high quality of the developed n-type hyperdoped material, which is single-phase single crystal with high electrical activation, without surface segregation of Se atoms and with an optically flat surface. [1] J. P. Mailoa, A. J. Akey, C. B. Simmons, D. Hutchinson, J. Mathews, J. T. Sullivan, D. Recht, M. T. Winkler, J. S. Williams, J. M. Warrender, P. D. Persans, M. J. Aziz, and T. Buonassisi, Nat. Commun. 5, 3011 (2014). [2] S. Zhou, F. Liu, S. Prucnal, K. Gao, M. Khalid, C. Baehtz, M. Posselt, W. Skorupa, and M. Helm, Sci. Rep. 5, 8329 (2015). [3] I. Umezu, J. M. Warrender, S. Charnvanichborikarn, A. Kohno, J. S. Williams, M. Tabbal, D. G. Papazoglou, X. C.Zhang, and M. J. Aziz, J. Appl. Phys. 113, 213501 (2013).

The development of room-temperature short-wavelength infrared Si photodetectors is of paramount importance for optical communications, integrated photonics, sensing and medical imaging applications [1]. The typical peak photoresponse of conventional Si photodetectors is between 700 and 900 nm, which is mainly limited by the 1.12 eV-Si indirect band gap. Nevertheless, such intrinsic material limitation can be circumvented by introducing transition metals or chalcogens into the Si band gap at concentrations far above those obtained at equilibrium conditions [1, 2]. This new class of hyperdoped materials with a donor impurity band has been postulated as a viable route to extend the Si photoresponse at the short-wavelength infrared spectral region [3]. In this work, we report on the significant room-temperature photoresponse and performance at wavelengths as long as 3100 nm as exhibited by hyperdoped Si p-n photodiodes fabricated by Se implantation followed by flash lamp annealing (FLA). The FLA approach in the millisecond range allows for a solid-phase epitaxy that has been reported to be superior to liquid-phase epitaxy induced during pulsed laser annealing [2]. The success of our devices is primarily based on the high quality of the developed n-type hyperdoped material, which is single-phase single crystal with high electrical activation, without surface segregation of Se atoms and with an optically flat surface. [1] J. P. Mailoa, A. J. Akey, C. B. Simmons, D. Hutchinson, J. Mathews, J. T. Sullivan, D. Recht, M. T. Winkler, J. S. Williams, J. M. Warrender, P. D. Persans, M. J. Aziz, and T. Buonassisi, Nat. Commun. 5, 3011 (2014). [2] S. Zhou, F. Liu, S. Prucnal, K. Gao, M. Khalid, C. Baehtz, M. Posselt, W. Skorupa, and M. Helm, Sci. Rep. 5, 8329 (2015). [3] I. Umezu, J. M. Warrender, S. Charnvanichborikarn, A. Kohno, J. S. Williams, M. Tabbal, D. G. Papazoglou, X. C.Zhang, and M. J. Aziz, J. Appl. Phys. 113, 213501 (2013)