Light-enhanced oxygen degradation of MAPbBr3 single crystal.

Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors. In this study, a methylammonium lead bromide (MAPbBr3) single crystal was cleaved and exposed to simultaneous oxygen and light illumination under ultrahigh vacuum (UHV). The exposure process was monitored using X-ray photoelectron spectroscopy (XPS) with precise control of the exposure time and oxygen pressure. It was found that the combination of oxygen and light accelerated the degradation of MAPbBr3, which could not be viewed as a simple addition of that by oxygen-only and light-only exposures. The XPS spectra showed significant loss of carbon, bromine, and nitrogen at an oxygen exposure of 1010 Langmuir with light illumination, approximately 17 times of the additive effects of oxygen-only and light-only exposures. It was also found that the photoluminescence (PL) emission was much weakened by oxygen and light co-exposure, while previous reports had shown that PL was substantially enhanced by oxygen-only exposure. Measurements using a scanning electron microscope (SEM) and focused ion beam (FIB) demonstrated that the crystal surface was much roughened by the co-exposure. Density functional theory (DFT) calculations revealed the formation of superoxide and oxygen induced gap state, suggesting the creation of oxygen radicals by light illumination as a possible microscopic driving force for enhanced degradation.

CuPc Passivation of a MAPbBr3 Single Crystal Surface.

In this study, a facile passivation for methylammonium lead bromide (MAPbBr3) single crystals is reported. Stability against moisture and light remains the most critical demerit of perovskite materials, which is improved by depositing a 40 Å thick hydrophobic copper phthalocyanine (CuPc) layer on top of the cleaved perovskite surface. The water and light exposure processes were monitored with X-ray photoelectron spectroscopy with precise control of the exposure time and pressure. It is found that the CuPc top layer could protect the sample from moisture infiltration at a water exposure of 1013 L, while the nonpassivated sample started to degrade at 108 L. During the light exposure, CuPc also slowed down the light-induced degradation, which is supported by the elemental ratio change of metallic lead and bromine. These results are further confirmed by the morphological comparison via scanning electron microscopy and focused ion beam.

Evaporation of Methylammonium Iodide in Thermal Deposition of MAPbI3.

Thermal evaporation is an important technique for fabricating methylammonium lead iodide (MAPbI3), but the process is complicated by the need to co-evaporate methylammonium iodide (MAI) and PbI2. In this work, the effect of water vapor during the thermal deposition of MAPbI3 was investigated under high vacuum. The evaporation process was monitored with a residual gas analyzer (RGA), and the film quality was examined with X-ray photoelectron spectroscopy (XPS). The investigations showed that during evaporation, MAI decomposed while PbI2 evaporated as a whole compound. It was found that the residual water vapor reacted with one of the MAI-dissociated products. The higher iodine ratio suggests that the real MAI flux was higher than the reading from the QCM. The XPS analysis demonstrated that the residual water vapor may alter the elemental ratios of C, N, and I in thermally deposited MAPbI3. Morphologic properties were investigated with atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). It was observed that a sample grown with high water vapor pressure had a roughened surface and poor film quality. Therefore, an evaporation environment with water vapor pressure below 10-8 Torr is needed to fabricate high quality perovskite films.

Reducing Surface Halide Deficiency for Efficient and Stable Iodide-Based Perovskite Solar Cells.

State-of-the-art, high-performance perovskite solar cells (PSCs) contain a large amount of iodine to realize smaller bandgaps. However, the presence of numerous iodine vacancies at the surface of the film formed by their evaporation during the thermal annealing process has been broadly shown to induce deep-level defects, incur nonradiative charge recombination, and induce photocurrent hysteresis, all of which limit the efficiency and stability of PSCs. In this work, modifying the defective surface of perovskite films with cadmium iodide (CdI2) effectively reduces the degree of surface iodine deficiency and stabilizes iodine ions via the formation of strong Cd-I ionic bonds. This largely reduces the interfacial charge recombination loss, yielding a high efficiency of 21.9% for blade-coated PSCs with an open-circuit voltage of 1.20 V, corresponding to a record small voltage deficit of 0.31 V. The CdI2 surface treatment also improves the operational stability of the PSCs, retaining 92% efficiency after constant illumination at 1 sun intensity for 1000 h. This work provides a promising strategy to optimize the surface/interface optoelectronic properties of perovskites for more efficient and stable solar cells and other optoelectronic devices.

Argon Plasma Treatment to Tune Perovskite Surface Composition for High Efficiency Solar Cells and Fast Photodetectors.

The surface composition of perovskite films is very sensitive to film processing and can deviate from the optimal, which generates unfavorable defects and results in efficiency loss in solar cells and slow response speed in photodetectors. An argon plasma treatment is introduced to modify the surface composition by tuning the ratio of organic and inorganic components as well as defect type before deposition of the passivating layer. It can efficiently enhance the charge collection across the perovskite-electrode interface by suppressing charge recombination. Therefore, perovskite solar cells with argon plasma treatment yield enhanced efficiency to 20.4% and perovskite photodetectors can reach their fastest respond speed, which is solely limited by the carrier mobility.

Valence band dispersion measurements of perovskite single crystals using angle-resolved photoemission spectroscopy.

The electronic structure of a cleaved perovskite (CH3NH3PbBr3) single crystal was studied in an ultra-high vacuum (UHV) system using angle-resolved photoemission spectroscopy (ARPES) and inverse photoelectron spectroscopy (IPES). Highly reproducible dispersive features of the valence bands were observed with symmetry about the Brillouin zone center and boundaries. The largest dispersion width was found to be ∼0.73 eV and ∼0.98 eV along the ΓX and ΓM directions, respectively. The effective mass of the holes was estimated to be ∼0.59m0. The quality of the surface was verified using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The elemental composition was investigated using high resolution X-ray photoelectron spectroscopy (XPS). The experimental electronic structure shows a good agreement with the theoretical calculation.