Organic photovoltaic cells possess desirable practical characteristics, such as the potential for low‐cost fabrication on flexible substrates, but they lag behind their inorganic counterparts in performance due in part to fundamental energy loss mechanisms, such as overcoming the charge transfer (CT) state binding energy when photogenerated charge is transferred across the donor/acceptor interface. However, recent work has suggested that crystalline interfaces can reduce this binding energy due to enhanced CT state delocalization. Solar cells based on rubrene and C60are investigated as an archetypal system because it allows the degree of crystallinity to be moldulated from a highly disordered to highly ordered system. Using a postdeposition annealing method to transform as‐deposited amorphous rubrene thin films into ones that are highly crystalline, it is shown that the CT state of a highly crystalline rubrene/C60heterojunction undergoes extreme delocalization parallel to the interface leading to a band‐like state that exhibits a linear Stark effect. This state parallels the direct charge formation of inorganic solar cells and reduces energetic losses by 220 meV compared with 12 other archetypal heterojunctions reported in the literature.
Mixed-dimensional van der Waals heterojunctions involve interfacing materials with different dimensionalities, such as a 2D transition metal dichalcogenide and a 0D organic semiconductor. These heterojunctions have shown unique interfacial properties not found in either individual component. Here, we use femtosecond transient absorption to reveal photoinduced charge transfer and interlayer exciton formation in a mixed-dimensional type-II heterojunction between monolayer MoS2 and vanadyl phthalocyanine (VOPc). Selective excitation of the MoS2 exciton leads to hole transfer from the MoS2 valence band to VOPc highest occupied molecular orbit in ∼710 fs. On the contrary, selective photoexcitation of the VOPc layer leads to instantaneous electron transfer from its excited state to the conduction band of MoS2 in less than 100 fs. This light-initiated ultrafast separation of electrons and holes across the heterojunction interface leads to the formation of an interlayer exciton. These interlayer excitons formed across the interface lead to longer-lived charge-separated states of up to 2.5 ns, longer than in each individual layer of this heterojunction. Thus, the longer charge-separated state along with ultrafast charge transfer times provide promising results for photovoltaic and optoelectronic device applications.
more » « less- Award ID(s):
- 2004420
- NSF-PAR ID:
- 10440281
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 18
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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