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In this paper, we present structural and luminescence studies of silicon-rich silicon oxide (SRO) and SRO-Si<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>3</mn> </msub> </semantics> </math> </inline-formula>N<inline-formula> <math display="inline"> <semantics> <msub> <mrow></mrow> <mn>4</mn> </msub> </semantics> </math> </inline-formula> bi-layers for integration in emitter-waveguide pairs that can be used for photonic lab-on-a-chip sensing applications. The results from bi and mono layers are also compared. Two clearly separated emission bands are respectively attributed to a combination of defect and quantum confinement&#8315;related emission in the SRO, as well as to defects found in an oxynitride transition zone that forms between the oxide and the nitride films, while ruling out quantum-confinement phenomena in the silicon nitride.