Improving efficiency and stability has become an urgent issue in the application of perovskite solar cells (PSCs). Herein, a kind of long‐chain polymer or polymethylmethacrylate (PMMA) is added into the spiro‐OMeTAD matrix to improve the film formation process and hence the device performance. It is observed that, after modification, the spiro‐OMeTAD‐based hole‐transporting layer becomes uniform, continuous, and condensed. Meanwhile, the power conversion efficiency of the devices is upgraded. Compared with the control device, open‐circuit voltage of the modified one (with moderate doping) increases from 1.06 (±0.03) to 1.10 (±0.02) V, fill factor increases from 72.20 (±3.44)% to 75.59 (±3.35)%, and the power conversion efficiency increases from 18.82 (±1.06)% to 20.51 (±0.82)% (highest at 21.78%) under standard test condition (AM 1.5G, 100 mW cm−2). Transient photocurrent/photovoltage decay curves, time‐resolved photoluminance, and impedance spectroscopy studies show that the modification could accelerate charge transfer and retard interfacial recombination. In addition, the modification improves device stability. Due to the strengthened barrier against penetration of “H2O/O2/Ag,” the efficiency of the unsealed device could retain 91.49% (by average) of the initial one after 100 days storage in the dark [relative humidity = 30(±5)%]. This work shows that long‐chain polymer doping could simultaneously improve efficiency and stability of spiro‐OMeTAD‐based PSCs.

Capsaicin is used to modify SnO2 quantum dots and then used as an electron-transfer material for perovskite solar cells. After capsaicin modification, the power conversion efficiency of the devices increases from 19.90 (± 0.47)% to 21.87 (± 0.28)% with a champion device of 22.24% (AM 1.5G, 100 mW/cm2). Transient photovoltage and photocurrent decay show that, after the capsaicin doping, the lifetime increases from 21.55 (± 1.54) to 27.63 (± 1.45)  μs, while the charge extraction time reduces from 1.90 (± 0.09) to 1.67 (± 0.06)  μs. Time-resolved photoluminescence and impedance spectrum studies show similar results. The accelerated charge transfer and retarded recombination are due to defect passivation. Space charge limited current study shows that, after modification, the trap density of devices is reduced from 2.24 × 1015 to 1.28 × 1015 cm−3. X-ray photoelectron spectroscopy and theoretical calculation indicate that the reduced trap density is due to the chemical interaction between carbonyl group (from capsaicin) and Sn atom, and that between carbonyl group and Pb atom.

Hydrophobic and long-chain molecule oleylamine is used to modify the spiro-OMeTAD matrix, which is then adopted for the hole-transport layer in perovskite solar cells. It is observed that after moderate doping, the power conversion efficiency of the devices increases from 17.82 (±1.47)% to 20.68 (±0.77)%, with the optimized efficiency of 21.57% (AM 1.5G, 100 mW/cm2). The improved efficiency is ascribed to the favored charge extraction and retarded charge recombination, as reflected by transient photovoltage/photocurrent curves and impedance spectroscopy measurement. In addition, the grazing incidence photoluminescence spectrum reveals that oleylamine doping causes a blue shift of the luminescence peak of the surface layer of the halide perovskite film, while the Mott−Schottky study observes 100 mV increment in the built-in potential, both of which indicate possible defect passivation behavior on the perovskite. Moreover, an accelerated damp test observes that moisture resistance of the device is also upgraded, which is due to the improved hydrophobicity of the spiro-OMeTAD matrix.