Light Emitting Properties of Si-Rich-Si3N4 Films Grown By PECVD Method

Bandgap engineering of Si-based materials through the control of the distribution of Si nanoclusters’ (Si-ncs) offered future applications of Si-based nanostructured materials in optoelectronics as low-cost, miniaturized, and CMOS-compatible, light-emitting and photovoltaic devices. In the past, most efforts were concentrated on the development of luminescent Si-ncs embedded in SiO₂ host. However, its insulating nature remains a barrier for the production of future electrically pumped LEDs and efficient photovoltaic cells. This detrimental aspect can be coped with a medium of higher conductivity and lower band gap, for instance, Si nitride. Tunable room temperature visible light emission from Si-ncs embedded in Si nitride matrices has been recently demonstrated.

Present work deals with the Si-rich Silicon nitride films were grown by PECVD technique on silicon substrates. The film stoichiometry was controlled via variation of NH₃/SiH₄ ratio from R=0.45 up to 1.0. Thermal treatment was performed at 1100°C for 30min in nitrogen flow to form Si-ncs. To control structural and light emitting properties of the films Raman scattering, X-ray diffraction (XRD), Transmission electron microscopy (TEM) and photoluminescence (PL) methods were used. The evolution of PL spectra with the temperature of measurements from 20 to 300 K was studied also aiming at the determination of the types of optical transitions. 

The PL spectra were found to be complex and the shape and magnitude of PL spectra depends on silicon nitride stoichiometry. The increase of gas ratio from R=0.63 to R=1 results in the shift of PL peak position from 1.6 eV up to 2.7 eV. Analysis of the temperature dependence of PL spectra revealed the presence of several PL components with the maxima at 2.9-3.0 eV, 2.5-2.7 eV, 1.9-2.2 eV and 1.8-1.9 eV. The peak position of the former three PL components unchanged with the decrease of temperature of the measurements. This allows describing all these components to the defects of silicon nitride host. At the same time, PL band peaked at 1.8-1.9 eV showed high-energy shift with sample cooling and can be ascribed to the exciton recombination inside Si-ncs. The presence of these latter was confirmed by Raman scattering spectra and TEM images. The nature of light emitting defects in silicon nitride, the mechanism of photoluminescence and the way for the optimization of light emitting properties are discussed.