Cu₂Se, owing to its intrinsic excellent thermoelectric (TE) performance emerging from the peculiar nature of “liquid-like” Cu⁺ ions, has been regarded as one of the most promising thermoelectric materials recently. However, the commercial use is still something far from reach unless effective approaches can be applied to further increase the figure of merit (ZT) of Cu₂Se, and doping has shown wide development prospect. Until now, the highest ZT value of 2.62 has been achieved in Al doped samples, which is twice as much as the original pure Cu₂Se. Herein, various doping elements from all main groups and some transitional groups that have been used as dopants in enhancing the TE performance of Cu₂Se are summarized, and the mechanisms of TE performance enhancement are analyzed. In addition, points of great concern for further enhancing the TE performance of doped Cu₂Se are proposed.

Thermoelectric technology can achieve mutual conversion between thermoelectricity and has the unique advantages of quiet operation, zero emissions and long life, all of which can help overcome the energy crisis. However, the large-scale application of thermoelectric technology is limited by its lower thermoelectric performance factor (ZT). The thermoelectric performance factor is a function of the Seebeck coefficient, electrical conductivity, thermal conductivity and absolute temperature. Since these parameters are interdependent, increasing the ZT value has always been a challenge. Here, we report the growth of Cu₂Se thin films with a thickness of around 100 nm by magnetron sputtering. XRD and TEM analysis shows that the film is low-temperature α-Cu₂Se, XPS analysis shows that about 10% of the film’s surface is oxidized, and the ratio of copper to selenium is 2.26:1. In the range of 300–400 K, the maximum conductivity of the film is 4.55 × 10⁵ S m⁻¹, which is the maximum value reached by the current Cu₂Se film. The corresponding Seebeck coefficient is between 15 and 30 µV K⁻¹, and the maximum ZT value is 0.073. This work systematically studies the characterization of thin films and the measurement of thermoelectric properties and lays the foundation for further research on nano-thin-film thermoelectrics.