Perovskite solar cells employing CH3NH3PbI3-xClx active layers show power conversion efficiency (PCE) as high as 20% in single cells and 13% in large area modules. However, their operational stability has often been limited due to degradation of the CH3NH3PbI3-xClx active layer. Here, we report a perovskite solar module (PSM, best and av. PCE 10.5 and 8.1%), employing solution-grown TiO2 nanorods (NRs) as the electron transport layer, which showed an increase in performance (∼5%) even after shelf-life investigation for 2500 h. A crucial issue on the module fabrication was the patterning of the TiO2 NRs, which was solved by interfacial engineering during the growth process and using an optimized laser pulse for patterning. A shelf-life comparison with PSMs built on TiO2 nanoparticles (NPs, best and av. PCE 7.9 and 5.5%) of similar thickness and on a compact TiO2 layer (CL, best and av. PCE 5.8 and 4.9%) shows, in contrast to that observed for NR PSMs, that PCE in NPs and CL PSMs dropped by ∼50 and ∼90%, respectively. This is due to the fact that the CH3NH3PbI3-xClx active layer shows superior phase stability when incorporated in devices with TiO2 NR scaffolds.

The size-dependent physicochemical and optical properties of silica nanoparticles have been studied. Significant increase in the specific surface area (SSA), concentration of silanol groups (δOH) and apparent density (Da) were observed as the particle size reduced from ∼130 to ∼7 nm. The decrease in the silanol number (αOH) and Si-O-Si bond angle in smaller particle size suggest that the silica structure, especially the surface has been significantly altered at nanoscale. This finding is supported by the presence of defect sites such as E′ centers and oxygen deficient centers (OCD). The stability of E′ centers (UV-vis analysis) increase linearly with the increase in particle size. The increase in the intensity of blue and green bands (PL analysis) with the decrease in the particle size are attributed to the higher silanol concentration and increased in the number of self-trapped exciton (STE)/OCD, respectively. The green band was blue-shifted with the decrease in the particle size. Overall, the silica nanoparticles have shown distinctive properties relative to the bulk silica.

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Grafting of free maleimide and epoxide pendant groups onto the surface of approximately 7-nm silica nanoparticles was investigated. Glycidyloxypropyl groups (3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) that carried epoxide groups and aminopropyl groups were grafted to the silica surface with the help of condensation reactions. Maleimide groups [1,1(')-(methylenedi-4,1-phenelene) bismaleimide] were introduced to the silica surface via nucleophilic addition reaction with the aminopropyl groups pre-grafted onto the surface. The grafted silica samples were characterized using CHN, FTIR, DSC, TGA-FTIR, and 13C and 29Si CP/MAS NMR spectroscopy. NMR analyses revealed that all the functional groups were covalently bonded to the silica surface and most of the maleimide and epoxide rings remained intact on surface. DSC analysis showed that the epoxide groups were more reactive than the maleimide groups.