In this work, we prepared four star-shaped conjugated small molecules, the triphenylamine dithiophene (TBT) derivatives, namely TBT-H, TBT-Br, TBT-OH, and TBT-N-3 presenting hydride, bromide, hydroxyl, and azide terminal functional groups, respectively. These TBT derivatives were used as additives in the active layers of organic photovoltaics to investigate the effect of intermolecular interactions (TBT-H, TBT-OH) or crosslinking (TBT-N-3, TBT-Br) on the long-term thermal stability of the devices. From analyses of blend film morphologies, and optoelectronic and device performance, we observed significant enhancements in thermal stability during accelerated heating tests at 150 degrees C for the devices incorporated with the additives TBT-N-3 and TBT-Br. These two additives functioned as crosslinkers, and constructed local borders that effectively impeded heat-promoted fullerene aggregation, thereby leading to highly stable morphologies. When compared with corresponding normal devices, the TBT-N-3-derived devices based on poly(3-hexylthiophene) exhibited greater stability, with the power conversion efficiency (PCE) remaining as high as 2.5% after 144h at 150 degrees C. Because of this enhancement, a device based on an amorphous low-bandgap polymer, namely poly(thieno[3,4-b]thiophene-alt-benzodithiophene), with the addition of TBT-N3 was fabricated. We observed a significant improvement in device stability, retaining approximately 60% (from 5.0 to 3.3%) of its initial PCE under accelerated heating (150 degrees C). In contrast, the PCE of the corresponding normal device decayed to 0.01% of its initial value. (C) 2016 Elsevier B.V. All rights reserved.