In this study, we employed explicit solvent simulations to design ligand-solvent systems for small-sized NCs with hydrocarbon tail ligands in nonpolar solvents, aiming to explore the effects of different ligands and solvents on the ligand shell structures and interparticle interactions. Our findings demonstrate that when molecular fragments (DB, BC, BR, NR) are positioned at the head or middle of the ligand chain, the ligands are disordered on the NC surface, which induces repulsive interparticle interactions. In contrast, when these fragments are located at the end of the ligand tail, the ligands form more ordered bundles, leading to attractive interactions. The PMF curves of NC pairs exhibit a double-well shape, and the two well minima correspond to the touch and lock contact modes. Our results indicate that the attraction in the touch mode is closely related to the order of the ligand bundle and can be weakened by adjusting the fragment position or introducing BC or DB in the middle of the ligand chain. The attraction in the lock mode is influenced by the number of solvent molecules penetrating the gaps between NCs, and can be modulated by altering the size of the solvent molecules.