In Situ Surface Fluorination of TiO2 Nanocrystals Reinforces Interface Binding of Perovskite Layer for Highly Efficient Solar Cells with Dramatically Enhanced Ultraviolet-Light Stability.

Low-temperature solution-processed TiO2 nanocrystals (LT-TiO2) have been extensively applied as electron transport layer (ETL) of perovskite solar cells (PSCs). However, the low electron mobility, high density of electronic trap states, and considerable photocatalytic activity of TiO2 result in undesirable charge recombination at the ETL/perovskite interface and notorious instability of PSCs under ultraviolet (UV) light. Herein, LT-TiO2 nanocrystals are in situ fluorinated via a simple nonhydrolytic method, affording formation of Ti─F bonds, and consequently increase electron mobility, decrease density of electronic trap states, and inhibit photocatalytic activity. Upon applying fluorinated TiO2 nanocrystals (F-TiO2) as ETL, regular-structure planar heterojunction PSC (PHJ-PSC) achieves a champion power conversion efficiency (PCE) of 22.68%, which is among the highest PCEs for PHJ-PSCs based on LT-TiO2 ETLs. Flexible PHJ-PSC devices based on F-TiO2 ETL exhibit the best PCE of 18.26%, which is the highest value for TiO2-based flexible devices. The bonded F atoms on the surface of TiO2 promote the formation of Pb─F bonds and hydrogen bonds between F- and FA/MA organic cations, reinforcing interface binding of perovskite layer with TiO2 ETL. This contributes to effective passivation of the surface trap states of perovskite film, resulting in enhancements of device efficiency and stability especially under UV light.

Fast Wetting of a Fullerene Capping Layer Improves the Efficiency and Scalability of Perovskite Solar Cells.

Fullerene derivatives, especially [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), have been widely applied as electron transport layers of inverted planar heterojunction perovskite solar cells (PSCs). However, the solution-processed PCBM capping layer suffers from limited surface wetting which hinders the improvement in efficiency and scalability of PSCs. Herein, we develop a facile hybrid solvent strategy that enables very fast wetting of the PCBM capping layer atop of the perovskite surface, leading to an improved interfacial contact and electron transport. The significantly enhanced wettability of the PCBM solution fulfilled through blending isopropyl alcohol into the commonly used chlorobenzene (CB) is attributed to the reduced surface tension while retaining viscosity. As a result, the electron mobility and electric conductivity of the PCBM capping layer increase by around two times, and the PSC devices exhibit the highest power conversion efficiency (PCE) of 19.92%, which is improved by ∼18% relative to that of the control device (16.78%). Importantly, this strategy is also applicable for other alcohols (ethanol and methanol) and CB blends. Moreover, the fast wetting approach enables us to deposit the PCBM capping layer using a facile drop-casting method, affording comparable PCEs to those obtained by the conventional spin-coating method, which is not achievable by using the conventional single solvent. This fast wetting PCBM capping layer also contributes to efficiency improvement of large-area (1 cm2) devices. These advances hold great potential for other scalable deposition methods such as blade-coating and slot-die coating.

Modifying Mesoporous TiO2 by Ammonium Sulfonate Boosts Performance of Perovskite Solar Cells.

Mesoporous-structure perovskite solar cells (meso-PVKSCs) have been widely utilized due to the achieved high efficiency for which the TiO2 layer usually suffers from sufficient electron trap states, low electron mobility, and inavoidable catalytic activity. Herein, a mesoporous TiO2 (m-TiO2) layer is modified by tetraethylammonium p-toluenesulfonate (abbreviated as TEATS) for the first time, leading to a significant photoelectric conversion efficiency enhancement from 19.14 to 20.69% for Cs0.05MA0.12FA0.83PbI2.55Br0.45 (abbreviated as CsMAFA) meso-PVKSCs. In particular, the obtained champion open-circuit voltage (Voc) is 1.18 V, which is a record high value for meso-PVKSCs with CsMAFA triple cation mixed perovskite. A series of measurements were employed to investigate the influences of TEATS modification on the energy band structures of TiO2 as well as the CsMAFA perovskite layer atop, unveiling that TEATS modification benefits defect passivation of the TiO2 film along with a decrease in the work function of TiO2. Besides, TEATS modification helps to improve the wettability of perovskite precursors on the m-TiO2 substrate, affording improved film quality of perovskite with enhanced crystallinity and grain size. Consequently, the trap states existed in the perovskite film can be passivated, and the interfacial charge recombination is suppressed. This further benefits the improvement of the ambient stability of devices.

Low-Temperature In Situ Amino Functionalization of TiO2 Nanoparticles Sharpens Electron Management Achieving over 21% Efficient Planar Perovskite Solar Cells.

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%. Cs0.05 FA0.83 MA0.12 PbI2.55 Br0.45 (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.