Optical spectroscopy study of silicon nanocrystals

Silicon nanocrystals (NCs), especially Si NCs embedded in SiO₂, have been studied intensely for decades for their potential application in silicon photonics, especially as efficient room temperature light emitters. Despite progress in fabricating photonic devices from Si NCs, the origin of the efficient photoluminescence (PL), the electronic and microscopic structure of the nanocrystals, and the structure of the elusive NC/SiO₂ interfaces for the oxide-embedded nanocrystals, remain controversial. Optical spectroscopy provides a powerful noninvasive tool for probing the structure of the Si NCs, including the active buried NC/SiO₂ interfaces of embedded particles. In this thesis work, oxide-embedded and free-standing alkyl-passivated silicon nanocrystals, prepared by different techniques, have been studied by linear and nonlinear optical spectroscopies. Cross-polarized 2-beam second-harmonic and sum-frequency generation (XP2-SHG/SFG) has been applied spectroscopically to study oxide embedded Si NCs of different sizes (3 to 5 nm diameter) and interface chemistries. The SHG/SFG spectra of silicon nanocrystals (Si NCs) prepared by implanting Si ions uniformly into silica substrates, then annealing, are compared and contrasted to their spectroscopic ellipsometric (SE) and photoluminescence excitation (PLE) spectra. Three resonances--two close in energy to E₁ (3.4 eV) and E2 (4.27 eV) critical-point resonances of crystalline silicon (c-Si), and a broad resonance intermediate in energy between E₁ and E₂--are observed in all three types of spectra. These features are observed in conjunction with a sharp 520 cm⁻¹ Raman peak characteristic of c-Si and an a-Si tail in the Raman spectra. The appearance of bulk-like CP resonances in the parallel PLE, SE and SHG/SFG spectra from Si NCs suggests the basic electronic structure of the bulk c-Si is preserved in nano-particles as small as 3 nm in diameter, albeit with significant size-dependent modification. At the same time, the prominence of a non-bulk-like resonance intermediate in energy between E₁ and E₂ CPs in all three types of spectra demonstrates the important contribution of nano-interfaces to the electronic structure.We also applied Raman spectroscopy to study oxide-embedded and oxide-free alkyl-passivated Si NCs with diameters ranging from 3 nm to greater than 10 nm synthesized by thermal decomposition of hydrogen silsesquioxane (HSQ). While oxide matrix complicates the size-dependence of the Raman peak shift for oxide-embedded nanocrystals, the Raman peak of the free-standing alkyl-passivated Si NCs shifts monotonically with NC size.