Patrick Mc Kearney

Hyperdoped germanium (Ge) has demonstrated increased sub-bandgap absorption, offering potential applications in the short-wavelength-infrared spectrum (1.0–3.0 μm). This study employs ion implantation to introduce a high concentration of selenium (Se) into Ge and investigates the effects of post-implantation annealing techniques on the recovery of implantation damage and alterations in optical properties. We identify optimal conditions for two distinct annealing techniques: rapid thermal annealing (RTA) at a temperature of 650 °C and ultrafast laser heating (ULH) at a fluence of 6 mJ/cm2. The optimized ULH process outperforms the RTA method in preserving high doping profiles and achieving a fourfold increase in sub-bandgap absorption. However, RTA leads to regrowth of single crystalline Ge, while ULH most likely leads to polycrystalline Ge. The study offers valuable insights into the hyperdoping processes in Ge for the development of advanced optoelectronic devices.

Charge carrier lifetime is a crucial material parameter in optoelectronic devices and knowing the dominant recombination channels points the way for improvements. The effective carrier lifetime τ_eff of surface‐passivated hyperdoped (hSi) and nonhyperdoped “black” (bSi) silicon by quasi‐steady‐state photoconductance decay (QSSPC) measurements and its evolution upon controlled wet‐chemical etching are studied. Sample preparation involves the irradiation of Si by numerous ultrashort laser pulses either in SF₆ for hSi or ambient atmosphere for bSi. Findings suggest that the hSi is composed of a double layer: 1) an amorphous resolidified top layer with about 92% of the total incorporated sulfur that accounts for the sub‐bandgap absorptance and 2) a crystalline layer underneath in which sulfur concentration tails off toward the Si substrate. The effective lifetime is deconstructed by a 1D simulation to quantify the impact of the local lifetime of the defect‐rich top layer, τ_top. It is found that by the QSSPC method, a maximum τ_top for 1) can be estimated. For 2), τ_top between 2 and 8 ns is estimated. The bSi sample shows a faster lifetime recovery upon etching which suggests that in hSi samples purely laser‐induced defects are not limiting the carrier lifetime compared to sulfur‐related defects.

The impact of three different pulse durations (100 fs, 1, and 10 ps) on the formation of laser hyperdoped black silicon with respect to surface morphology, sub‐bandgap absorptance, the sulfur concentration profile, and the effective minority carrier lifetime after Al₂O₃ surface passivation is investigated. The current flow behavior is compared through the hyperdoped layer by I–V measurements after hyperdoping with different pulse durations. For conditions that give the same absolute sub‐bandgap absorptance, an increase in pulse duration from 100 fs to 10 ps results in a shallower sulfur concentration profile. Findings are explained by an increasing ablation threshold from 0.19 J cm⁻² for a pulse duration of 100 fs to 0.21 J cm⁻² for 1 ps and 0.34 J cm⁻² for 10 ps. The formation of an equally absorbing layer with a shallower doping profile results in a reduction in contact and/or sheet resistance. Despite the higher local sulfur concentration, the samples show no decrease in carrier lifetime measured by quasi‐steady‐state photoconductance decay on Al₂O₃ surface‐passivated samples. The investigation shows that longer pulses of up to 10 ps during laser hyperdoping of silicon result in advanced layer properties that promise to be beneficial in a potential device application.

Crystalline silicon becomes photosensitive and absorbing in the sub-bandgap spectral region if hyperdoped, i.e. supersaturated to a level above the solubility limit in thermal equilibrium, by deep impurities, such as sulfur. Here we apply femtosecond laserpulses to crystalline silicon in a SF₆ atmosphere as hyperdoping method. The ultrashort laser pulses cause crystal damage and amorphous phases that would decrease quantum efficiency in a potential optoelectronic device application. We investigate five different post-hyperdoping methods: three etching techniques (ion beam etching IBE, reactive ion etching RIE, and wet-chemical etching HNA) as well as ns-annealing and minute-long thermal annealing and study their impact on crystallinity by Raman spectroscopy and absorptance in the visible and near infrared wavelength regime. We use femtosecond laser hyperdoped silicon (fs-hSi) with two different levels of surface roughness to study a potential dependence on the impact of post-treatments. In our investigation, ns-annealing leads to the best results, characterized by a high Raman crystallinity and a high remaining absorptance in the sub-bandgap spectral region of silicon. Within the used etching methods IBE outperforms the other etching methods above a certain level of fs-hSi surface roughness. We relate this to the specific anisotropic material removal behavior of the IBE technique and back this up with simulations of the effect of the various etching processes.

Ultrashort pulse laser processed sulfur hyperdoped black silicon represents a promising silicon-based material for infrared optoelectronic applications due to its high sub-bandgap optical absorptance. Non-thermal melting and resolidification processes associated with such laser processing, however, result in amorphous and polycrystalline phases which may be detrimental for this purpose. Furthermore, the sulfur impurities are electrically inactive, impeding the formation of a rectifying junction. This work demonstrates an ultrafast laser heating process based on heat accumulation with laser pulses of 10 ps pulse duration at high repetition rates of 41 MHz and peak fluences between 33% and 66% of the ablation threshold as a method to (i) recrystallize the material and (ii) electrically activate the sulfur dopants while (iii) maintaining the sub-bandgap absorption. Furthermore, laser heating recovers the optical activity of sulfur states that have been previously deactivated by thermal annealing. The demonstrated process can have versatile applications in material functionalization due to its highly localized heat input accompanied by high cooling rates.

Femtosecond laser sulfur hyperdoped silicon (fs-hSi) is capable of absorbing photons in the infrared spectral range while simultaneously exhibiting negligible reflection. However, laser processing creates detrimental amorphous and polycrystalline silicon surface layers impairing electronic properties, especially reducing minority charge carrier lifetimes. This paper demonstrates how to selectively remove these disadvantageous layers by ion beam etching, while crystalline IR-absorbing silicon underneath is left. The increase in silicon crystallinity is quantified by laterally probing the fs-hSi samples with Raman spectroscopy.