The use of non-fullerene acceptors in organic photovoltaic (OPV) devices could lead to enhanced efficiencies due to increased open-circuit voltage (VOC) and improved absorption of solar light. Here we systematically investigate planar heterojunction devices comprising peripherally substituted subphthalocyanines as acceptors and correlate the device performance with the heterojunction energetics. As a result of a balance between VOC and the photocurrent, tuning of the interface energy gap is necessary to optimize the power conversion efficiency in these devices. In addition, we explore the role of the charge transport layers in the device architecture. It is found that non-fullerene acceptors require adjusted buffer layers with aligned electron transport levels to enable efficient charge extraction, while the insertion of an exciton-blocking layer at the anode interface further boosts photocurrent generation. These adjustments result in a planar-heterojunction OPV device with an efficiency of 6.9% and a VOC above 1 V.

Four hexachlorosubphthalocyanines SubPcCl 6 -X bearing different axial substituents (X) have been synthesized for use as novel electron acceptors in solution-processed bulkheterojunction organic solar cells.S ubphthalocyanines are aromatic chromophoric molecules with cone-shaped structure, good solution processability,i ntense optical absorption in the visible spectral region, appropriate electron mobilities,a nd tunable energy levels.S olar cells with subphthalocyanines as the electron acceptor and PTB7-Th as the electron donor exhibit apower conversion efficiency up to 4%and an external quantum efficiency approaching 60 %d ue to significant contributions from both the electron donor and the electron acceptor to the photocurrent, indicating ap romising prospect of non-fullerene acceptors based on subphthalocyanines and structurally related systems.

An optimization of several aspects of planar heterojunction solar cells based on boron subnaphthalocyanine chloride (SubNc) as a donor material is presented. The use of hexachlorinated boron subphthalocyanine chloride (Cl6SubPc) as an alternative acceptor to C60 allows for the simultaneous increase of the short‐circuit current, fill factor, and open‐circuit voltage compared to cells with fullerene acceptors. This is due to the complementary absorption of Cl6SubPc versus SubNc, reduced recombination at the heterointerface, and improved energetic alignment. Furthermore, insertion of a thin diindeno[1,2,3‐cd:1′,2′,3′‐lm]perylene (DIP) layer at the anode results in a very significant 60% increase in photocurrent owing to reduced exciton quenching at the anode. The simultaneous improvement of all three solar cell para­meters results in a power conversion efficiency of 6.4% for a non‐fullerene planar heterojunction cell.

A series of peripherally dicyano-, tricyano-, and tetracyano-substituted subphthalocyanines (SubPcs) have been prepared through microwave-assisted, palladium-mediated cyanation of iodinated precursors. The introduction of π-accepting cyano groups in the macrocycle clearly influences its electronic and redox properties, which are dependent on the number and relative position of these substituents. Additional functionalization of the periphery of SubPcs with electron-donating or -withdrawing groups allows for a further fine-tuning of their features, leading to intensely absorbing, strongly electron-accepting panchromatic dyes with low-lying LUMO energy levels. Flash-photolysis time-resolved microwave conductivity measurements on vapor-deposited films demonstrate that some of these novel SubPc derivatives display remarkable intrinsic charge-carrier mobilities that are comparable to or larger than those of other known well-performing acceptor SubPcs; thus confirming their potential as n-type organic semiconductors for application in the fabrication of photovoltaic devices.

Unsymmetrical subphthalocyanine fused dimers have been prepared, resulting in unprecedented push–pull π-extended curved aromatic macrocycles.