Memory and ferroelectric photovoltaic effects arising from quasi-reversible oxidation and reduction in porphyrin entrapped aminopropyl-silicate films

• Prophyrin derivatives entrapped aminopropyl-silicate films were prepared by sol–gel method.
• The silicate films show bipolar switching and non-zero-crossing current–voltage characteristics.
• The open circuit voltage and short circuit current have been utilized to read the ON and OFF states for non-volatile memory applications.
• The redox induced polarization of the film exhibits ferroelectric photovoltaic characteristics.

We report non-zero-crossing bipolar current–voltage characteristics, and ferroelectric photovoltaic-like effects in flexible organosilicate polymer films. These film are composed of 5,10,15,20-terakis(4-hydroxyphenyl)-21H,23H-porphine and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine embedded in (3-aminopropyl)trimethoxysilane network. The films were prepared on gold coated bi-axially oriented polyethylene terephthalate (BoPET) substrate by sol–gel method. For electrical characterizations, gold (40 nm) was deposited on the film for using as top contact. The current–voltage characteristics of devices, BoPET/gold/film/gold, have shown hysteresis with two current peaks in opposite direction. The open circuit voltage (∼±0.8 V) and short circuit current (∼±6 μA) that arise from non zero-crossing current–voltage characteristics have been utilized to read the ON and OFF states for non-volatile memory application of the devices. Furthermore, the studies on redox induced polarization in the polymer matrix by charge–voltage, capacitance–voltage, and positive-up and negative-down measurements reveal the characteristics of ferroelectric materials. The photovoltaic behaviors such as short circuit photocurrent were studied under blue LED source after polarizing BoPET/gold/polymer film/gold device by electric field as done for classical ferroelectric materials. The observed memory, ferroelectric-like and photovoltaic effects of organosilicate film were explained from quasi-reversible oxidation and reduction of moisture that diffuse into the film and dissociate to ions under applied electric field. These findings are important for designing new solution processible polymer materials which could find applications in flexible memory, ferroelectric based memory and switchable photovoltaic effects.

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