Optical and electronic coupling of the redox copper Azurin on ITO-coated quartz substrate

We have investigated the hybrid system constituted by the redox copper protein Azurin integrated with the semiconductor indium tin oxide (ITO) coated on quartz substrate. The system appears to be a good candidate for bio-sensing and bio-optoelectronics applications, especially due to the coupling between the optical and electron transfer features of Azurin with the conductive properties and optical transparency of ITO. The optical, morphological and electrical properties of the system have been investigated by combining optical absorption and transmission, steady-state fluorescence, resonance Raman spectroscopy and scanning probe microscopies. We found that Azurin molecules are firmly anchored on ITO and retain their structural and optical features underlying the physiological electron transfer activity. Scanning tunnelling spectroscopy evidenced a good electric coupling between the protein molecules and the substrate and a concomitant modulation of the ITO semiconductor properties upon deposition of Azurin. Some interplay between the conduction and valence bands of ITO and the electronic levels of Azurin is therefore suggested. These results are of a significant relevance in the perspective of developing bio-nanodevices able to process both optical and electrical signals, in conjugation also with the biorecognition capability of the protein molecules.