Takeshi Sugita

Degradation mechanism of CH3NH3PbI3 perovskite materials upon exposure to humid air

Low stability of organic-inorganic perovskite (CH3NH3PbI3) solar cells in humid air environments is a serious drawback which could limit practical application of this material severely. In this study, from real-time spectroscopic ellipsometry characterization, the degradation mechanism of ultra-smooth CH3NH3PbI3 layers prepared by a laser evaporation technique is studied. We present evidence that the CH3NH3PbI3 degradation in humid air proceeds by two competing reactions of (i) the PbI2 formation by the desorption of CH3NH3I species and (ii) the generation of a CH3NH3PbI3 hydrate phase by H2O incorporation. In particular, rapid phase change occurs in the near-surface region and the CH3NH3PbI3 layer thickness reduces rapidly in the initial 1 h air exposure even at a low relative humidity of 40%. After the prolonged air exposure, the CH3NH3PbI3 layer is converted completely to hexagonal platelet PbI2/hydrate crystals that have a distinct atomic-scale multilayer structure with a period of 0.65 ± 0.05 nm. We ...

Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction

We analyzed the crystallization process of the CH3NH3PbI3 perovskite by observing real-time X-ray diffraction immediately after combining a PbI2 thin film with a CH3NH3I solution. A detailed analysis of the transformation kinetics demonstrated the fractal diffusion of the CH3NH3I solution into the PbI2 film. Moreover, the perovskite crystal was found to be initially oriented based on the PbI2 crystal orientation but to gradually transition to a random orientation. The fluctuating characteristics of the crystallization process of perovskites, such as fractal penetration and orientational transformation, should be controlled to allow the fabrication of high-quality perovskite crystals. The characteristic reaction dynamics observed in this study should assist in establishing reproducible fabrication processes for perovskite solar cells.

Universal rules for visible-light absorption in hybrid perovskite materials

A variety of organic-inorganic hybrid perovskites (APbX3) consisting of mixed center cations [A = CH3NH3+, HC(NH2)2+, and Cs+] with different PbX3− cages (X = I, Br, and Cl) have been developed to realize high-efficiency solar cells. Nevertheless, clear understanding of the effects of A and X on the optical transition has been lacking. Here, we present universal rules that allow the unified interpretation of the optical absorption in various hybrid perovskites. In particular, we find that the influence of the A-site cation on the light absorption is rather significant and the absorption coefficient (α) reduces to half when CH3NH3+ is replaced with HC(NH2)2+ in the APbI3 system. Our density functional theory calculations reproduce all of the fine absorption features observed in HC(NH2)2PbI3 and CH3NH3PbBr3, allowing the unique assignment of the interband transitions in the Brillouin zone. In contrast to general understanding that the A-site cation involves weakly in the optical process, our theoretical cal...

Laser deposition for the controlled co-deposition of organolead halide perovskite

A laser deposition system for the co-evaporation of organolead halide perovskite was developed. We successfully demonstrated that the difficulty in deposition control of CH3NH3I (MAI) was overcome by laser deposition, where the evaporation rate was finely adjusted by tuning the duty ratio of squarely modulated infrared laser. Deposition rate was stabilized for several-hour co-deposition period. The laser deposition method enabled the stoichiometric control of MAI and PbI2 with sufficient reproducibility. Planar type perovskite solar cells were constructed with the use of p-type and n-type organic semiconductor as buffer layers and the efficiency of 16.0 % with reduced hysteresis was achieved.