Titanium oxide (TiO2) has been commonly used as an electron transport layer (ETL) of regular‐structure perovskite solar cells (PSCs), and so far the reported PSC devices with power conversion efficiencies (PCEs) over 21% are mostly based on mesoporous structures containing an indispensable mesoporous TiO2 layer. However, a high temperature annealing (over 450 °C) treatment is mandatory, which is incompatible with low‐cost fabrication and flexible devices. Herein, a facile one‐step, low‐temperature, nonhydrolytic approach to in situ synthesizing amino‐functionalized TiO2 nanoparticles (abbreviated as NH2‐TiO2 NPs) is developed by chemical bonding of amino (‐NH2) groups, via TiN bonds, onto the surface of TiO2 NPs. NH2‐TiO2 NPs are then incorporated as an efficient ETL in n‐i‐p planar heterojunction (PHJ) PSCs, affording PCE over 21%. Cs0.05FA0.83MA0.12PbI2.55Br0.45 (abbreviated as CsFAMA) PHJ PSC devices based on NH2‐TiO2 ETL exhibit the best PCE of 21.33%, which is significantly higher than that of the devices based on the pristine TiO2 ETL (19.82%) and is close to the record PCE for devices with similar structures and fabrication procedures. Besides, due to the passivation of the surface trap states of perovskite film, the hysteresis of current–voltage response is significantly suppressed, and the ambient stability of devices is improved upon amino functionalization.

An amphiphilic surfactant, oleamide, was applied to dope the PCBM electron transport layer (ETL) of inverted structure perovskite solar cells (ISPSCs), resulting in a dramatic efficiency enhancement. Under the optimized oleamide doping ratio of 5.0 wt %, the power conversion efficiency of the CH3NH3PbIxCl(3-x) perovskite-based ISPSC device is enhanced from 10.05% to 12.69%, and this is primarily due to the increases of both fill factor and short-circuit current. According to the surface morphology study of the perovskite/PCBM bilayer film, oleamide doping improves the coverage of PCBM ETL onto the perovskite layer, and this is beneficial for the interfacial contact between the perovskite layer and the Ag cathode and consequently the electron transport from perovskite to the Ag cathode. Such an improved electron transport induced by oleamide doping is further evidenced by the impedance spectroscopic study, revealing the prohibited electron-hole recombination at the interface between the perovskite layer and the Ag cathode.

Inorganic metal oxide, especially TiO, has been commonly used as an electron transport layer (ETL) in regular-structure (n-i-p) planar heterojunction perovskite solar cells (PHJ-PSCs) but generally suffers from high electron recombination rate and incompatibility with low-temperature solution processability. Herein, by applying an ionic liquid (IL, 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]PF)) as either a TiO-modifying interlayer or an independent ETL, we investigated systematically IL interface engineering for PHJ-PSCs. Upon spin-coating [EMIM]PF-IL onto TiO ETL as a modification layer, the average power conversion efficiency (PCE) of CHNHPbI PHJ-PSC devices reaches 18.42 ± 0.65%, which dramatically surpasses that based on commonly used TiO ETL (14.20 ± 0.43%), and the highest PCE (19.59%) is almost identical to that of the record PCE for planar CHNHPbI PSCs (19.62%) reported very recently. On the other hand, by applying [EMIM]PF-IL as an independent ETL, we achieved an average PCE of 13.25 ± 0.55%, and the highest PCE (14.39%) approaches that obtained for PHJ-PSCs based on independent TiO ETL (14.96%). Both IL interface engineering methods reveal the effective electron transport of [EMIM]PF-IL. The effects of [EMIM]PF-IL on the surface morphology, crystallinity, and optical absorption of the perovskite film and the interface between the perovskite layer and substrate were investigated and compared with the case of independent TiO ETL, revealing the role of [EMIM]PF-IL in efficient electron transport.

Kesterite-structured quaternary semiconductor Cu2ZnSnS4 (CZTS) has been commonly used as light absorber in thin film solar cells on the basis of its optimal bandgap of 1.5 eV, high absorption coefficient, and earth-abundant elemental constituents. Herein we applied CZTS nanoparticles as a novel inorganic hole transporting material (HTM) for organo-lead halide perovskite solar cells (PSCs) for the first time, achieving a power conversion efficiency (PCE) of 12.75%, which is the highest PCE for PSCs with Cu-based inorganic HTMs reported up to now, and quite comparable to that obtained for PSCs based on commonly used organic HTM such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD). The size of CZTS nanoparticles and its incorporation condition as HTM were optimized, and the effects of CZTS HTM on the optical absorption, crystallinity, morphology of the perovskite film and the interface between the perovskite layer and the Au electrode were investigated and compared with the case of spiro-MeOTAD HTM, revealing the role of CZTS in efficient hole transporting from the perovskite layer to the top Au electrode as confirmed by the prohibited charge recombination at the perovskite/Au electrode interface. On the basis of the effectiveness of CZTS as a low-cost HTM competitive to spiro-MeOTAD in PSCs, we demonstrate the new role of CZTS in photovoltaics as a hole conductor beyond the traditional light absorber.

No abstract

A new successive surface engineering method via a dual modification of TiO2 compact layer by PC61BM and C60-ETA was developed, affording dramatic efficiency enhancement with suppressed-hysteresis current–voltage response.

A two-step method has been popularly adopted to fabricate a perovskite film of planar heterojunction organo-lead halide perovskite solar cells (PSCs). However, this method often generates uncontrollable film morphology with poor coverage. Herein, we report a facile method to improve perovskite film morphology by incorporating a small amount of acetate (CH3COO(-), Ac(-)) salts (NH4Ac, NaAc) as nonhalogen additives in CH3NH3I solution used for immersing PbI2 film, resulting in improved CH3NH3PbI3 film morphology. Under the optimized NH4Ac additive concentration of 10 wt %, the best power conversion efficiency (PCE) reaches 17.02%, which is enhanced by ∼23.2% relative to that of the pristine device without additive, whereas the NaAc additive does not lead to an efficiency enhancement despite the improvement of the CH3NH3PbI3 film morphology. SEM study reveals that NH4Ac and NaAc additives can both effectively improve perovskite film morphology by increasing the surface coverage via diminishing pinholes. The improvement on CH3NH3PbI3 film morphology is beneficial for increasing the optical absorption of perovskite film and improving the interfacial contact at the perovskite/spiro-OMeTAD interface, leading to the increase of short-circuit current and consequently efficiency enhancement of the PSC device for NH4Ac additive only.

Organometal halide CHNHPbI (MAPbI) has been commonly used as the light absorber layer of perovskite solar cells (PSCs), and, especially, another halide element chlorine (Cl) has been often incorporated to assist the crystallization of perovskite film. However, in most cases, a predominant MAPbI phase with trace of Cl is obtained ultimately and the role of Cl involvement remains unclear. Herein, we develop a low-cost and facile method, named hydrochloric acid vapor annealing (HAVA) post-treatment, and realize a rapid conversion of MAPbI to phase-pure MAPbCl, demonstrating a new concept of phase engineering of perovskite materials toward efficiency enhancement of PSCs for the first time. The average grain size of perovskite film after HAVA post-treatment increases remarkably through an Ostwald ripening process, leading to a denser and smoother perovskite film with reduced trap states and enhanced crystallinity. More importantly, the generation of MAPbCl secondary phase via phase engineering is beneficial for improving the carrier mobility with a more balanced carrier transport rate and enlarging the band gap of perovskite film along with optimized energy level alignment. As a result, under the optimized HAVA post-treatment time (2 min), we achieved a significant enhancement of the power conversion efficiency (PCE) of the MAPbI-based planar heterojunction-PSC device from 14.02 to 17.40% (the highest PCE reaches 18.45%) with greatly suppressed hysteresis of the current-voltage response.