Abstract
Hybrid metal-halide perovskites have emerged as leading class of semiconductors for photovoltaic devices with remarkable light harvesting efficiencies. The formation of methylammonium lead iodide (CH3NH3PbI3) perovskite into mesoporous titania (TiO2) scaffold by a sequential deposition technique is known to offer better control over the perovskite morphology. The growth reactions at the mesoporous TiO2 film depend on reactants concentration in the host matrix and the reaction activation energy. Here, we are characterizing formation of CH3NH3PbI3 perovskite in mimic solar cell photoelectrodes utilizing the developed NanoPlasmonic Sensing (NPS) approach. Based on dielectric changes at the TiO2 mesoporous film interface, the technique provides time-resolved spectral shifts of the localized surface plasmon resonance that varies widely depending on the different operating temperatures and methylammonium iodide (CH3NH3I) concentrations. Analytical studies included Ellipsometry, Scanning Electron Microscopy, and X-ray diffraction. The results show that perovskite conversion can be obtained at lower CH3NH3I concentrations if reaction activation energy is lowered. A significant finding is that the NPS response at 350 nm mesoporous TiO2 can widely change from red shifts to blue shifts depending on extent of conversion and morphology of perovskite formed at given reaction conditions.
Highlights
Inorganic-organic hybrid halide perovskites have shown great potential for a breakthrough of generation solar devices.[1,2,3,4,5,6,7] Lead-based and lead-free perovskites have been studied in terms of crystal structure, thin film deposition and device performance by theoretical calculations and experimental studies.[8]
Rajab et al[25] used nanoplasmonic sensing (NPS) to detect CH3NH3PbI3 perovskite formation at the interface of thick TiO2 films with Au nanodisks, where complete conversion of perovskite formation was characterized by slow NanoPlasmonic Sensing (NPS) red shifts while incomplete reactions were characterized by fast methylammonium iodide (CH3NH3I) crystallization
Standard films comprising of fused silica coated with Au nanodisks (100 nm diameter and 20 nm height) and 10 nm dense layer of compact TiO2 as a dielectric spacer layer were used to analyze the nanoplasmonic sensing of Au nanosensors, similar to the early studied NPS experimental system arrangements.[26,27,28,29]
Summary
Inorganic-organic hybrid halide perovskites have shown great potential for a breakthrough of generation solar devices.[1,2,3,4,5,6,7] Lead-based and lead-free perovskites have been studied in terms of crystal structure, thin film deposition and device performance by theoretical calculations and experimental studies.[8]. Rajab et al[25] used nanoplasmonic sensing (NPS) to detect CH3NH3PbI3 perovskite formation at the interface of thick TiO2 films with Au nanodisks, where complete conversion of perovskite formation was characterized by slow NPS red shifts while incomplete reactions were characterized by fast methylammonium iodide (CH3NH3I) crystallization. When complete reaction activation energies were reduced, perovskite formation was characterized by relatively fast NPS red shifts. Rajab et al demonstrate the capability to use the fast, minute and varying NPS changes to detect the formation kinetics of CH3NH3PbI3 perovskite at the lower interface of thin mesoporous TiO2 films. We assess the perovskite structures according to their formation kinetics and analytical results obtained by the characterization techniques
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