Photoferroelectric perovskite solar cells: Principles, advances and insights

Two organolead halide perovskite nanocrystals, CH(3)NH(3)PbBr(3) and CH(3)NH(3)PbI(3), were found to efficiently sensitize TiO(2) for visible-light conversion in photoelectrochemical cells. When self-assembled on mesoporous TiO(2) films, the nanocrystalline perovskites exhibit strong band-gap absorptions as semiconductors. The CH(3)NH(3)PbI(3)-based photocell with spectral sensitivity of up to 800 nm yielded a solar energy conversion efficiency of 3.8%. The CH(3)NH(3)PbBr(3)-based cell showed a high photovoltage of 0.96 V with an external quantum conversion efficiency of 65%.

Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation.

High efficiency perovskite solar cells were fabricated reproducibly via Lewis base adduct of lead(II) iodide. PbI2 was dissolved in N,N-dimethyformamide with equimolar N,N-dimethyl sulfoxide (DMSO) and CH3NH3I. Stretching vibration of S═O appeared at 1045 cm(-1) for bare DMSO, which was shifted to 1020 and 1015 cm(-1) upon reacting DMSO with PbI2 and PbI2 + CH3NH3I, respectively, indicative of forming the adduct of PbI2·DMSO and CH3NH3I·PbI2·DMSO due to interaction between Lewis base DMSO and/or iodide (I(-)) and Lewis acid PbI2. Spin-coating of a DMF solution containing PbI2, CH3NH3I, and DMSO (1:1:1 mol %) formed a transparent adduct film, which was converted to a dark brown film upon heating at low temperature of 65 °C for 1 min due to removal of the volatile DMSO from the adduct. The adduct-induced CH3NH3PbI3 exhibited high charge extraction characteristics with hole mobility as high as 3.9 × 10(-3) cm(2)/(V s) and slow recombination rate. Average power conversion efficiency (PCE) of 18.3% was achieved from 41 cells and the best PCE of 19.7% was attained via adduct approach.