Organometal halide perovskites are highly promising materials for photovoltaic applications, yet their rapid degradation remains a significant challenge. Here, the light-induced structural degradation mechanism of methylammonium lead iodide (MAPbI3) perovskite films and devices is studied in low humidity environment using X-Ray Diffraction, Ultraviolet-Visible (UV-Vis) absorption spectroscopy, Extended X-ray Absorption Fine Structure spectroscopy, Fourier Transform Infrared spectroscopy, and device measurements. Under dry conditions, the perovskite film degrades only in the presence of both light and oxygen, which together induce the formation of halide anions through donation of electrons to the surrounding oxygen. The halide anions generate free radicals that deprotonate the methylammonium cation and form the highly volatile CH3NH2 molecules that escape and leave pure PbI2 behind. The device findings show that changes in the local structure at the TiO2 mesoporous layer occur with light, even in the absence of oxygen, and yet such changes can be prevented by the application of UV blocking layer on the cells. Our results indicate that the stability of mp-TiO2-MAPbI3 photovoltaics can be dramatically improved with effective encapsulation that protects the device from UV light, oxygen, and moisture.
Here we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3 ) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We now show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.
The atomic layer deposition (ALD) of ZnS films with Zn(TMHD)2 and in situ generated H2S as precursors was investigated, over a temperature range of 150–375 °C. ALD behavior was confirmed by investigation of growth behavior and saturation curves. The properties of the films were studied with atomic force microscopy, scanning electron microscopy, energy-dispersive x-ray spectroscopy, ultraviolet–visible–infrared spectroscopy, and extended x-ray absorption fine structure. The results demonstrate a film that can penetrate a porous matrix, with a local Zn structure of bulk ZnS, and a band gap between 3.5 and 3.6 eV. The ZnS film was used as a buffer layer in nanostructured PbS quantum dot solar cell devices.
Multilayer film stacks of ZnS and Cu x S (x $ 2) were made via atomic layer deposition. The precursors were bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc, bis(2,2,6,6-tetramethyl-3,5heptanedionato)copper, and H 2 S generated in situ for sulfur. Samples were deposited at 200 C, in layers ranging from approximately 2 to 20 nm thick, based on binary growth rates. The properties of the film stacks were studied with atomic force microscopy, ultraviolet-visible spectroscopy, and extended x-ray absorption fine structure. The results demonstrate that the structure of films with the thinnest layers is dominated by Cu x S, whereas in the thicker films, the structure is determined by whichever material is first deposited. This can be attributed to the crystal structure mismatch of ZnS and Cu x S. V
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