Density functional theory investigation of opto-electronic properties of thieno[3,4-b]thiophene and benzodithiophene polymer and derivatives and their applications in solar cell

•Two different approaches are applied to carry out the theoretical investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method.•Substitution of nitrogen and oxygen atoms in the benzodithiophene (BDT) unit of pristine PTB7 while silicon, phosphorous, and selenium atoms are substituted in thieno thiophene (TT) unit can improve the maximum theoretical efficiencies (MTE) in donor/PC71BM performances.•Substitution of sulfur by nitrogen and oxygen atoms in the benzodithiophene (BDT) unit lead to a significant improvement in difference between the ground and excited states in local dipole moment of one monomer of PTB7 derivatives.

PTBs polymers with thieno[3,4-b]thiophene [TT] and benzodithiophene [BDT] units have particular properties, which demonstrate it as one of the best group of donor materials in organic solar cells. In the present work, density functional theory (DFT) is applied to investigate the optimized structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), band gap and dihedral angle of PTB7 at B3LYP/6-31G(d). Two different approaches are applied to carry out these investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method. The results obtained from PBC-DFT method are in fair agreement with experiments. Based on these reliable outcomes; the investigations continued to perform some derivatives of PTB7. In this study, sulfur is substituted by nitrogen, oxygen, silicon, phosphor or selenium atoms in pristine PTB7. Due to the shift of HOMO and LUMO levels, smaller band gaps are predicted to appear in some derivatives in comparison with PTB7. Maximum theoretical efficiencies, η, of the mentioned derivatives as well as local difference of dipole moments between the ground and excited states (Δμge) are computed. The results indicate that substitution of sulfur by nitrogen or oxygen in BDT unit, and silicon or phosphor in TT unit of pristine PTB7 leads to a higher η as well as Δμge.

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