Person:

Recht, Daniel

Strong absorption of sub-band gap radiation by an impurity band has recently been demonstrated in silicon supersaturated with chalcogen impurities. However, despite the enhanced absorption in this material, the transformation of infrared radiation into an electrical signal via extrinsic photoconductivity—the critical performance requirement for many optoelectronic applications—has only been reported at low temperature because thermal impurity ionization overwhelms photoionization at room temperature. Here, dopant compensation is used to manipulate the optical and electronic properties and thereby improve the room-temperature infrared photoresponse. Silicon co-doped with boron and sulfur is fabricated using ion implantation and nanosecond pulsed laser melting to achieve supersaturated sulfur concentrations and a matched boron distribution. The location of the Fermi level within the sulfur-induced impurity band is controlled by tuning the acceptor-to-donor ratio, and through this dopant compensation, three orders of magnitude improvement in infrared detection at 1550 nm is demonstrated.

Intermediate-band materials have the potential to be highly efficient solar cells and can be fabricate by incorporating ultrahigh concentrations of deep-level dopants. Direct measurements of the ultrafast carrier recombination processes under supersaturated dopant concentrations have not been previously conducted. Here, we use optical-pump/terahertz-probe measurements to study carrier recombination dynamics of chalcogen-hyperdoped silicon with sub-picosecond resolution. The recombination dynamics is described by two exponential decay time scales: a fast decay time scale ranges between 1 and 200ps followed by a slow decay on the order of 1 ns. In contrast to the prior theoretical predictions, we find that the carrier lifetime decreases with increasing dopant concentration up to and above the insulator-to-metal transition. Evaluating the material’s figure of merit reveals an optimum doping concentration for maximizing performance.

Silicon supersaturated with sulfur by ion implantation and pulsed laser melting exhibits broadband optical absorption of photons with energies less than silicon's band gap. However, this metastable, hyperdoped material loses its ability to absorb sub-band gap light after subsequent thermal treatment. We explore this deactivation process through optical absorption and electronic transport measurements of sulfur-hyperdoped silicon subject to anneals at a range of durations and temperatures. The deactivation process is well described by the Johnson-Mehl-Avrami-Kolmogorov framework for the diffusion-mediated transformation of a metastable supersaturated solid solution, and we find that this transformation is characterized by an apparent activation energy of (E_A=1.7 ± 0.1  eV). Using this activation energy, the evolution of the optical and electronic properties for all anneal duration-temperature combinations collapse onto distinct curves as a function of the extent of reaction. We provide a mechanistic interpretation of this deactivation based on short-range thermally activated atomic movements of the dopants to form sulfur complexes.

Tin monosulfide (SnS) is of interest as a potential solar cell absorber material. We present a preliminary investigation of the effects of sputtering conditions on SnS thin-film structural, optical, and electronic properties. Films were RF sputtered from an SnS target using an argon plasma. Resistivity, stoichiometry, phase, grain size and shape, bandgap, and optical absorption coefficient can be varied by modifying argon pressure for a fixed deposition time. Most films have an indirect bandgap in the range of 1.08–1.18 eV. XRD patterns confirmed the films as mostly crystalline, and grain morphology was examined using profile and surface SEM images.

Highly supersaturated solid solutions of selenium or sulfur in silicon were formed by ion implantation followed by nanosecond pulsed laser melting. n+p photodiodesfabricated from these materials exhibit gain (external quantum efficiency >3000%) at 12 V of reverse bias and substantial optoelectronic response to light of wavelengths as long as 1250 nm. The amount of gain and the strength of the extended response both decrease with decreasing magnitude of bias voltage, but >100% external quantum efficiency is observed even at 2 V of reverse bias. The behavior is inconsistent with our expectations for avalanche gain or photoconductive gain.

Hyperdoping has emerged as a promising method for designing semiconductors with unique optical and electronic properties, although such properties currently lack a clear microscopic explanation. Combining computational and experimental evidence, we probe the origin of sub–band-gap optical absorption and metallicity in Se-hyperdoped Si. We show that sub–band-gap absorption arises from direct defect– to–conduction-band transitions rather than free carrier absorption. Density functional theory predicts the Se-induced insulator-to-metal transition arises from merging of defect and conduction bands, at a concentration in excellent agreement with experiment. Quantum Monte Carlo calculations confirm the critical concentration, demonstrate that correlation is important to describing the transition accurately, and suggest that it is a classic impurity-driven Mott transition.

Nanosecond melting and quenching of materials offers a pathway to novel structures with unusual properties. Impurity-rich silicon processed using nanosecond-pulsed-laser-melting is known to produce nanoscale features in a process referred to as “cellular breakdown” due to destabilization of the planar liquid/solid interface. Here, we apply atom probe tomography combined with electron microscopy to show that the morphology of cellular breakdown in these materials is significantly more complex than previously documented. We observe breakdown into a complex, branching filamentary structure topped by a few nm of a cell-like layer. Singlephase diamond cubic silicon highly supersaturated with at least 10% atomic Co and no detectable silicides is reported within these filaments. In addition, the unprecedented spatio-chemical accuracy of the atom probe allows us to investigate nanosecond formation dynamics of this complex material. Previously-reported properties of these materials can now be reconsidered in light of their true composition, and this class of inhomogeneous metastable alloys in silicon can be explored with confidence.