Intermediate Band Properties of Femtosecond-Laser Hyperdoped Silicon

Abstract

This thesis explores using femtosecond-laser pulses to hyperdope silicon with chalcogen dopants at concentrations above the maximum equilibrium solubility. Hyperdoped silicon is promising for improving efficiencies of solar cells: the material exhibits broad-band light absorption to wavelengths deep below the corresponding bandgap energy of silicon. The high concentration of dopants forms an intermediate band (IB), instead of discrete energy levels, and the IB enables sub-bandgap light absorption. This thesis is divided into two primary studies: the dopant incorporation and the IB properties. First, we study dopant incorporation with a gas-phase dopant precursor (SF6) using secondary ion mass spectrometry. By varying the pressure of SF6, we find that the surface adsorbed molecules are the dominant source of the dopant. Furthermore, we show the hyperdoped layer is single crystalline. The results demonstrate that the dopant incorporation depth, concentration, and crystallinity are controlled respectively by the number of laser pulses, pressure of the dopant precursor, and laser fluence. Second, we study the IB properties of hyperdoped silicon using optical and electronic measurements. We use Fourier transform infrared spectroscopy to study light absorption. The absorption extends to wavelengths as far as 6 μm before thermal annealing and we find the upper bound of the IB location at 0.2 eV below the conduction band edge. For electronic measurements, we anneal the samples to form a diode between the hyperdoped layer and the substrate, allowing us to probe the IB using temperature-dependent electronic transport measurements. The measurement data indicate that these samples form a localized IB at concentrations below the insulator-to-metal transition. Using a two-band model, we obtain the location of the localized IB at >0.07 eV below the conduction band edge. After femtosecond-laser hyperdoping, annealing is necessary to reduce the laser-induced defects; however annealing decreases the sub-bandgap absorption. As we are interested in the IB that contributes to sub-bandgap absorption, we explore methods to reactivate the sub-bandgap absorption. We show that the sub-bandgap absorption is reactivated by annealing at high temperatures between 1350 and 1550 K followed by fast cooling (>50 K/s). Our results demonstrate an ability to control sub-bandgap absorption using thermal processing.