A simple protocol to study the dynamics of charge transfer to selective contacts in perovskite solar cells, based on time-resolved laser spectroscopy studies, in which the effect of bimolecular electron-hole recombination has been eliminated, is proposed. Through the proposed procedure, the interfacial charge-transfer rate constants from methylammonium lead iodide perovskite to different contact materials can be determined. Hole transfer is faster for CuSCN (rate constant 0.20 ns(-1) ) than that for 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD; 0.06 ns(-1) ), and electron transfer is faster for mesoporous (0.11 ns(-1) ) than that for compact (0.02 ns(-1) ) TiO2 layers. Despite more rapid charge separation, the photovoltaic performance of CuSCN cells is worse than that of spiro-OMeTAD cells; this is explained by faster charge recombination in CuSCN cells, as revealed by impedance spectroscopy. The proposed direction of studies should be one of the key strategies to explore efficient hole-selective contacts as an alternative to spiro-OMeTAD.
Direct
laser writing (DLW) lithography has emerged as a competitive
additive tool for the fabrication of detailed three-dimensional (3D)
structures with a minimum feature size close to the nanometer scale.
However, the minimal distance between adjacently written features
with no overlapping, that is the writing resolution, is not in the
same scale as the feature size. This is a consequence of the so-called
“memory effect”, namely, the accumulation of radicals
between polymerized structures, which prevents the development of
DLW for commercial applications. To overcome these limitations, we
propose an original approach based on the reversible formation of
the active species triggering the polymerization to decrease the impact
of the “memory effect” on the writing resolution. We
have selected the [6,6]-phenyl-C61-butyric acid methyl
ester (PCBM) molecule as the cationic photoinitiator in combination
with an oxidizing agent, AgPF6, to trigger the polymerization
of the photoresist. The two-photon absorption (2PA) ability of the
PCBM material was explored by using the open aperture z-scan technique,
obtaining a 2PA cross-section of ∼400 GM. We have also utilized
pump–probe spectroscopy to demonstrate the formation of the
radical cation of the PCBM via a photoinduced electron transfer reaction
with the Ag+ cation (ΔG < 0).
Moreover, the regeneration of the primary photoinitiating system PCBM/AgPF6 was investigated with the flash photolysis technique, proving
the absence of excited species in the μs time scale. This is
the key point of our approach: the reversible character of the electron
transfer process allows the partial regeneration of the primary photoinitiator
in the interstice between polymerized structures avoiding the “memory
effect”. The implementation of this approach with commonly
used resists, SU-8 or Araldite, has resulted in a notable improvement
of the spatial resolution, from 600 to 400 nm when using a conventional
photoinitiator compared to our PCBM/AgPF6 system.
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