10.1002/anie.201909117
Angewandte Chemie International Edition
COMMUNICATION
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absence of methoxy groups and excellent film quality make the
doped devices based on M129 more stable than M130 under
ambient air. The M129 device can retain 94% of their original
PCEs after 800 h with a humidity of 30% and the PCE slightly
decreased to 82% of the initial value at 1000 h as the humidity
increased to 40% (Figure 4d). In contrast, the M130 device
dropped well below 65% of their original performance. The lower
environmental stability of M130 could be attributed to the
hydrophilicity of methoxy groups, which resulted in a smaller
water contact angle of 73o with respect to M129 (84.3°, Figure
S28). In addition, high Tg value of M129 is beneficial to the thermal
stability of PSCs. The PCE of dopant-free M129 was maintained
at 90% of the original value after thermal stress at 60 °C for 72 h
under N2 atmosphere (Figure S29). A slight degradation was
observed after thermal stress at 70 °C. In contrast, the device
made with doped Spiro-OMeTAD exhibited apparent degradation
when thermal annealing was applied from 60o to 70o. This result
can be ascribed to deformation of the Spiro-OMeTAD film arising
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In summary, this work focuses on the HTM dilemma between
achieving both high efficiency and stability. We constructed a
methoxy-free donor alternative to MOTPA by fusing the fluorene
into carbazole. Introduction of dimethylfluoren is found to improve
the morphology uniformity and hole extraction. Moreover,
expanding the donor raises the Tg of HTM by around 70 oC. Due
to distinct advantages in Tg, hole mobility, film morphology and
processability, M129 with the indeno[1,2-b]carbazole realized a
high efficiency and stability simultaneously. The doped M129
exhibits a PCE exceeding 20% and the dopant-free device shows
a PCE greater than 17%. The values are commensurate with
current best results among doped and dopant-free organic HTMs
for n-i-p structured PSCs. The hybrid strategy toward methoxy-
free donor gets rid of the restriction of MOTPA as the electron
donor in the designing efficient doped and dopant-free organic
HTMs, opening a new avenue for developing efficient and stable
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Keywords: hole-transporting materials • perovskites solar cells•
methoxy-free donor • hybrid donor • indeno[1,2-b]carbazole
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