Methods development and measurements for understanding morphological effects on electronic and optical properties in solution processable photovoltaic materials
Ostrowski, David Paul
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The effects of morphology on electronic and optical properties in solution processable photovoltaic (PV) materials have been studied through two different approaches. One approach, scanning photocurrent (PC) and photoluminescence (PL) microscopy, involved mapping PC generation and PL in functional PV devices on the length scale of around 250-500 nm. Additionally, local diode characteristics were studied from regions of interest in the PV through local voltage-dependent photocurrent (LVPC) measurements. In a PV made from a Copper Indium Gallium Selenide (CIGS) nanocrystal (NC) "ink", two morphological features were found to cause the spatial heterogeneity in PC generation. Cadmium Sulfide (CdS) aggregates lowered PC generation by blocking incident light to the photoactive layer, and cracks in the CIGS-NC film enhanced PC generation through improved charge carrier extraction. LVPC measurements showed all regions to have similar diode characteristics with the main difference being the PC generated at zero bias voltage. For another PV made from a donor/acceptor blend of poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,Nphenyl- 1,4-phenylenediamine (PFB) and poly(9,9-dioctylfluorene-co-benzothiadiazole)(F8BT), two incident laser wavelengths were used to selectively illuminate only one or both polymers. The results showed that when F8BT is illuminated, the PFB-rich regions produced the most PC and when both polymers are illuminated (but mostly PFB), the F8BT-rich regions produce the most PC; showing PC generation is more affective when less absorber material is present in the morphology. The other approach to study morphological effects on PV properties was to fabricate particles that mimicked morphological variations known to occur in solution-processable PVs. Through solution processing of an oligothiophene molecule, a range of weakly coupled H-aggregate particles were made. These particles, identifiable by shape, were shown to have a varying degree of energetic disorder (as gauged by the 0-0 vibronic band intensity in the emission spectrum), despite all particles showing a similarly high degree of molecular order from fluorescence dichroism (FD) measurements. A trend was observed correlating a decrease in energetic disorder with an increase in the local contact potential (LCP) difference as measured with Kelvin probe force microscopy (KPFM). The LCP difference was found to range by 70 mV between particles of moderate to low energetic disorder.