The previous works commonly adjust the carrier concentration through acceptor doping, but at the same time, the decrease of the Seebeck coefficient limits the further improvement of electrical properties in Cu₃SbSe₄-based materials. In this work, a microwave-assisted hydrothermal synthesis method was used to synthesize Cu₃SbSe₄/TiO₂ hollow microspheres. Part of TiO₂ participates in the reaction, replaces the Sb site of Cu₃SbSe₄ to form holes, and the rest is dispersed in the matrix in the form of the second phase. The first-principles calculations reveal that the doping of Ti significantly changes the band structure and phonon spectrum, thereby regulating carrier concentration while increasing phonon scattering. In addition, experimental results show that the energy filtering effect generated by the extra-mixed TiO₂ nano particles, which suppresses the decrease of Seebeck coefficient by acceptor doping. Consequently, the highest average power factor 897.5 μW m⁻¹ K⁻² and the zT peak value of 0.70 can be obtained in Cu₃SbSe₄/6%TiO₂ sample at 298–623 K. This work provides a new sight to improve the thermoelectric properties in Cu₃SbSe₄ through carrier concentration regulation and nano-phase composition.

以往的工作通常通过受主掺杂来调节载流子浓度，但同时塞贝克系数的降低限制了Cu ₃ SbSe ₄基材料电学性能的进一步提高。本工作采用微波辅助水热合成法合成了Cu ₃ SbSe ₄ /TiO ₂空心微球。部分TiO ₂参与反应，取代Cu ₃ SbSe _4的Sb位形成空穴，其余的以第二相的形式分散在基体中。第一性原理计算表明，Ti的掺杂显着改变了能带结构和声子光谱，从而在增加声子散射的同时调节载流子浓度。此外，实验结果表明，额外混合的TiO ₂纳米颗粒产生的能量过滤效应，抑制了受主掺杂对塞贝克系数的降低。_{因此，在Cu 3} SbSe ₄ /6%TiO ₂中可以获得最高的平均功率因数897.5 μW m ^-1  K ^-2和0.70的zT峰值样品在 298–623 K。这项工作为通过载流子浓度调节和纳米相组成改善 Cu ₃ SbSe ₄的热电性能提供了新的视角。