Effects of interfacial ligand type on hybrid P3HT:CdSe quantum dot solar cell device parameters

A series of CdSe quantum dot acceptors possessing six different ligand frameworks (i.e., pivalic acid, pyridine, butylamine, tert-butylthiol, thiophenol, and tetrahydrothiophene) were used as platforms for investigating the influence of quantum dot surface chemistry on the performance of hybrid poly(3-hexythiophene-2,5-diyl) (P3HT):CdSe quantum dot bulk heterojunction (BHJ) solar cells. We confirm that the device parameters used to evaluate solar cell performance are significantly influenced by the nature of the quantum dot surface ligand. The dependence of short circuit current density (J_SC) on the CdSe ligand type was probed using ultrafast time-resolved photoluminescence (PL) measurements, and good correlations between the ligand-dependent trends in J_SC and excited state lifetime were found, in which the P3HT:CdSe quantum dot BHJs with the shortest PL lifetimes possess the largest device current densities. The frontier energy levels of the quantum dot acceptors are significantly influenced by surface ligands, wherein the device open circuit potentials (V_OC) were found to linearly correlate with the energy difference (ΔE_DA) between the HOMO of the P3HT donor and the electrochemically determined LUMO of the CdSe quantum dot acceptors over a range of 220 mV. This work demonstrates the versatility of quantum dot ligand engineering for tuning the device parameters and performance of hybrid solar cells.