Effect of Copper Doping on Electronic Structure and Optical Absorption of Cd₃₃Se₃₃ Quantum Dots

The photophysical properties of Cu-doped CdSe quantum dots (QDs) can be affected by the oxidation state of Cu impurity, but disagreement still exists on the Cu oxidation state (+1 or +2) in these QDs, which is debated and poorly understood for many years. In this work, by using density functional theory (DFT)-based calculations with the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional, we clearly demonstrate that the incorporation of Cu dopants into the surface of the magic sized Cd₃₃Se₃₃ QD leads to non-magnetic Cu 3d orbitals distribution and Cu⁺¹ oxidation state, while doping Cu atoms in the core region of QDs can lead to both Cu⁺¹ and Cu⁺² oxidation states, depending on the local environment of Cu atoms in the QDs. In addition, it is found that the optical absorption of the Cu-doped Cd₃₃Se₃₃ QD in the visible region is mainly affected by Cu concentration, while the absorption in the infrared regime is closely related to the oxidation state of Cu. The present results enable us to use the doping of Cu impurity in CdSe QDs to achieve special photophysical properties for their applications in high-efficiency photovoltaic devices. The methods used here to resolve the electronic and optical properties of Cu-doped CdSe QDs can be extended to other II-VI semiconductor QDs incorporating transition-metal ions with variable valence.