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We observe an insulator-to-metal (I-M) transition in crystalline silicon doped with sulfur to non- equilibrium concentrations using ion implantation followed by pulsed laser melting and rapid resolidification. This I-M 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 x 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., Submission formatting; 4 journal pages equivalent

We report an experimental study of photocarrier lifetime, transport, and excitation spectra in silicon-on-insulator doped with sulfur far above thermodynamic saturation. The spectral dependence of photocurrent in coplanar structures is consistent with photocarrier generation throughout the hyperdoped and undoped sub-layers, limited by collection of holes transported along the undoped layer. Holes photoexcited in the hyperdoped layer are able to diffuse to the undoped layer, implying (μτ)h ∼ 5 × 10−9 cm2/V. Although high absorptance of hyperdoped silicon is observed from 1200 to 2000 nm in transmission experiments, the number of collected electrons per absorbed photon is 10−4 of the above-bandgap response of the device, consistent with (μτ)e < 1 × 10−7cm2/V.

Photoconductivity in silicon hyperdoped with sulfur and selenium above the insulator-to-metal transition was measured via photoinduced changes in the microwave reflectivity of hyperdoped layers formed on p-type silicon. Despite these materials' strong subgap optical absorption, exposing them to 1310 and 1550 nm light results in a change in conductivity per photon 10,000 times smaller than what is observed in untreated silicon exposed to 980 nm light. A similar bound applies for 405 nm light, which is absorbed entirely in the hyperdoped layer. We use these results to deduce that the photocarrier lifetime in the hyperdoped material is ≤100 ns.

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.

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.