Daniel Recht

Insulator-to-Metal Transition in Sulfur-Doped Silicon

We observe an insulator-to-metal transition in crystalline silicon doped with sulfur to nonequilibrium concentrations using ion implantation followed by pulsed-laser melting and rapid resolidification. This insulator-to-metal transition is due to a dopant known to produce only deep levels at equilibrium concentrations. Temperature-dependent conductivity and Hall effect measurements for temperatures T>1.7  K both indicate that a transition from insulating to metallic conduction occurs at a sulfur concentration between 1.8 and 4.3×10(20)  cm(-3). Conduction in insulating samples is consistent with variable-range hopping with a Coulomb gap. The capacity for deep states to effect metallic conduction by delocalization is the only known route to bulk intermediate band photovoltaics in silicon.

Insulator-to-Metal Transition in Selenium-Hyperdoped Silicon: Observation and Origin

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.

Extended infrared photoresponse and gain in chalcogen-supersaturated silicon photodiodes

Highly supersaturated solid solutions of selenium or sulfur in silicon were formed by ion implantation followed by nanosecond pulsed laser melting. n+p photodiodes fabricated 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.

Room-temperature sub-band gap optoelectronic response of hyperdoped silicon

Room-temperature infrared sub-band gap photoresponse in silicon is of interest for telecommunications, imaging and solid-state energy conversion. Attempts to induce infrared response in silicon largely centred on combining the modification of its electronic structure via controlled defect formation (for example, vacancies and dislocations) with waveguide coupling, or integration with foreign materials. Impurity-mediated sub-band gap photoresponse in silicon is an alternative to these methods but it has only been studied at low temperature. Here we demonstrate impurity-mediated room-temperature sub-band gap photoresponse in single-crystal silicon-based planar photodiodes. A rapid and repeatable laser-based hyperdoping method incorporates supersaturated gold dopant concentrations on the order of 10(20) cm(-3) into a single-crystal surface layer ~150 nm thin. We demonstrate room-temperature silicon spectral response extending to wavelengths as long as 2,200 nm, with response increasing monotonically with supersaturated gold dopant concentration. This hyperdoping approach offers a possible path to tunable, broadband infrared imaging using silicon at room temperature.

Enhanced visible and near-infrared optical absorption in silicon supersaturated with chalcogens

We show that single-crystal silicon supersaturated with sulfur (S), selenium (Se), or tellurium (Te) displays a substantially enhanced absorption coefficient for light with wavelengths of 400 to 1600 nm. Alloys were prepared in silicon on insulator wafers by ion implantation followed by nanosecond pulsed laser melting. Measurements of the absorption coefficient were made by direct transmission through freestanding thin films and by spectroscopic ellipsometry.

Supersaturating silicon with transition metals by ion implantation and pulsed laser melting

Research at Harvard was supported by The U.S. Army Research Office under contracts W911NF-12-1-0196 and W911NF-09-1-0118. M.T.W. and T.B.’s work was supported by the U.S. Army Research Laboratory and the U.S. Army Research Office under Grant No. W911NF-10-1-0442, and the National Science Foundation (NSF) Faculty Early Career Development Program ECCS-1150878 (to T.B.). M.J.S., J.T.S., M.T.W., T.B., and S.G. acknowledge a generous gift from the Chesonis Family Foundation and support in part by the National Science Foundation (NSF) and the Department of Energy (DOE) under NSF CA No. EEC- 1041895. S.C. and J.S.W.’s work was supported by The Australian Research Council. J.M. was supported by a National Research Council Research Associateship.

Soft x-ray emission spectroscopy studies of the electronic structure of silicon supersaturated with sulfur

We apply soft x-ray emission spectroscopy (XES) to measure the electronic structure of crystalline silicon supersaturated with sulfur (up to 0.7 at. %), a candidate intermediate-band solar cell material. Si L2,3 emission features are observed above the conventional Si valence band maximum, with intensity scaling linearly with S concentration. The lineshape of the S-induced features change across the insulator-to-metal transition, indicating a significant modification of the local electronic structure concurrent with the change in macroscopic electronic behavior. The relationship between the Si L2,3XESspectral features and the anomalously high sub-band gap infrared absorption is discussed.

Photocarrier lifetime and transport in silicon supersaturated with sulfur

Research at Rensselaer was supported by the Army Research Office under Contract No. W911NF0910470 and by the NSF REU program at Rensselaer. Research at Harvard was supported by US Army ARDEC under Contract No. W15QKN-07-P-0092. D.R. was supported in part by a National Defense Science and Engineering Graduate fellowship.

Controlling dopant profiles in hyperdoped silicon by modifying dopant evaporation rates during pulsed laser melting

We describe a method to control the sub-surface dopant profile in “hyperdoped” silicon fabricated by ion implantation and pulsed laser melting. Dipping silicon ion implanted with sulfur into hydrofluoric acid prior to nanosecond pulsed laser melting leads to a tenfold increase in the rate of sulfur evaporation from the surface of the melt. This results in an 80% reduction of the near-surface dopant concentration, effectively embedding the hyperdoped region in a layer up to 180 nm beneath the surface. This method should facilitate the development of blocked impurity band devices.

Picosecond carrier recombination dynamics in chalcogen-hyperdoped silicon

Intermediate-band materials have the potential to be highly efficient solar cells and can be fabricated 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 200 ps 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 materials figure of merit reveals an optimum doping concentration for maximizing performance.