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Semiconductor-metal heterojunction nanostructures possess an ability to store electrons upon photoexcitation through Fermi level equilibration. The unique role of capping ligands in modulating the equilibration of Fermi level in CdSe-Au heteronanostructures is explored by taking alkyl thiols and alkyl amines as examples. Alkyl thiol having its highest occupied molecular orbital (HOMO) above the valence band of the heterojunction nanostructure inhibits the exciton recombination by scavenging the photogenerated hole. This leads to the el