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Structural and optical characterization of pure Si-rich nitride thin films

Olivier Debieu1*, Ramesh Pratibha Nalini1, Julien Cardin1, Xavier Portier1, Jacques Perrière2 and Fabrice Gourbilleau1

Author affiliations

1 CIMAP, UMR 6252 CNRS-ENSICAEN-CEA-UCBN, Ensicaen, 6 Bd Maréchal Juin, 14050 Caen, cedex 4, France

2 UNIV PARIS 06, INSP NANOSCIENCE PARIS, CNRS, UMR 7588, 75015 Paris, France

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Citation and License

Nanoscale Research Letters 2013, 8:31  doi:10.1186/1556-276X-8-31

Published: 16 January 2013


The specific dependence of the Si content on the structural and optical properties of O- and H-free Si-rich nitride (SiNx>1.33) thin films deposited by magnetron sputtering is investigated. A semiempirical relation between the composition and the refractive index was found. In the absence of Si-H, N-H, and Si-O vibration modes in the FTIR spectra, the transverse and longitudinal optical (TO-LO) Si-N stretching pair modes could be unambiguously identified using the Berreman effect. With increasing Si content, the LO and the TO bands shifted to lower wavenumbers, and the LO band intensity dropped suggesting that the films became more disordered. Besides, the LO and the TO bands shifted to higher wavenumbers with increasing annealing temperature which may result from the phase separation between Si nanoparticles (Si-np) and the host medium. Indeed, XRD and Raman measurements showed that crystalline Si-np formed upon 1100°C annealing but only for SiNx<0.8. Besides, quantum confinement effects on the Raman peaks of crystalline Si-np, which were observed by HRTEM, were evidenced for Si-np average sizes between 3 and 6 nm. A contrario, visible photoluminescence (PL) was only observed for SiNx>0.9, demonstrating that this PL is not originating from confined states in crystalline Si-np. As an additional proof, the PL was quenched while crystalline Si-np could be formed by laser annealing. Besides, the PL cannot be explained neither by defect states in the bandgap nor by tail to tail recombination. The PL properties of SiNx>0.9 could be then due to a size effect of Si-np but having an amorphous phase.

Silicon nitride; Silicon nanocrystals; Amorphous silicon nanoparticles; FTIR; Raman; XRD; Laser annealing; Photoluminescence