Picosecond photoelectron spectroscopy of excited states at Si(111)√3 × √3R30°-B, Si(111)7×7, Si(100)2×1, and laser-annealed Si(111)1×1 surfaces

Photoelectron spectra resulting from sequential or simultaneous absorption of two photons have been studied at four different silicon surfaces. To study energy-relaxation lifetimes, one laser pulse populates conduction states and normally unoccupied surface states, from which photoelectrons are excited by the second pulse after a preset delay. Laser pulses of 1--3-ps duration in the energy range 2.33--4.66 eV are employed at repetition rates up to 82 MHz. Very high two-photon photoelectron-count rates are achieved with the methods described, while the sample temperature remains far below thresholds for melting, and space-charge effects are negligible. Surface states, particularly within the bulk band gap, are very prominent in these experiments. Hot-electron intermediate states above the conduction-band minimum (CBM) are observed, and two spectral features that persist on different surfaces are attributed to peaks in the density of conduction states of the bulk-band structure, specifically along {Λ} and at {Γ}. The near-surface population of electrons at the CBM is strongly limited by capture in surface states and by diffusion into the bulk. Photoelectron emission from the CBM excited by 4.0--4.66-eV photons is observed only by indirect transitions or scattering via surface states and defects.