The molecular orientation
of organic molecules of zinc phthalocyanine
(ZnPc) in single-component films on copper iodide (CuI) substrates
can be controlled to achieve a molecular orientation lying flat on
the substrate (flat-on) owing to π–d orbital interactions
between the ZnPc molecules and the CuI. A 3-fold enhancement in the
performance of organic photovoltaic cells has been reported by introducing
a CuI interlayer between a ZnPc:fullerene (C60) bulk heterojunction
(BHJ) film and the substrate. However, the mechanism underpinning
the resultant solar cell performance enhancement was unclear. Herein,
we report on the results of using in situ reflection absorption spectroscopy
measurements during the vacuum deposition of coevaporated ZnPc:C60
BHJ films on various substrates to investigate the ZnPc molecular
orientation. Our results revealed that the flat-on molecular orientation
of ZnPc molecules in ZnPc:C60 BHJ films on CuI interlayers and flat-on
ZnPc substrates can be successfully identified via the strong π–π
interactions between the BHJ film and the substrate. The π–π
interactions between individual ZnPc molecules are stronger than the
π–d interactions between ZnPc molecules and CuI in coevaporated
ZnPc:C60 films, as is evident from the molecular orientation of ZnPc,
as determined by in situ reflection absorption spectroscopy. Our findings
demonstrate that precisely controlling the molecular orientations
of the films could enhance organic photovoltaic (OPV) performance.
The present work provides important insights that will enable the
design of higher performance OPV cells.
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