Herein, three hybrids of metal Phthalocyanine complexes (MPc, M=Ni, Cu, Co) with single-walled carbon nanotubes (SWCNTs) were prepared by ball milling combined with cold pressing method and their thermoelectric (TE) properties were studied. The electrical conductivity of the MPc/SWCNT hybrids remarkably increased with increasing SWCNT content and was higher than the values calculated based on the mixture rule, whereas the Seebeck coefficient slightly decreased in the whole range. Moreover, the NiPc/SWCNT hybrids showed higher electrical conductivity than those of CuPc/SWCNT and CoPc/SWCNT hybrids. It is demonstrated by Raman analyses and energy level measurement that strong donor-acceptor interactions occur between MPc and SWCNTs. Such interactions may promote the carrier transport at the interface, and therefore increase the carrier mobility resulting in the enhancement of electrical conductivity greatly overstepping the mixture rule. Furthermore, among the three hybrids, the interface energy barrier of NiPc/SWNT hybrids is the lowest, which also contributes to the high electrical conductivity. Finally, the maximum electrical conductivity and thermoelectric power factor of NiPc/SWCNT hybrids are up to 540 S cm⁻¹ and 120 μWm⁻¹ K⁻² respectively, which is 30–50% higher than those of CuPc/SWCNT and CoPc/SWCNT hybrids and among the best level of metal-organic small molecules based TE materials.

在此，通过球磨结合冷压法制备了三种金属酞菁配合物（MPc，M=Ni，Cu，Co）与单壁碳纳米管（SWCNTs）的杂化物及其热电(TE) 特性进行了研究。MPc/SWCNT 杂化物的电导率随着 SWCNT 含量的增加而显着增加，并且高于根据混合规则计算的值，而塞贝克系数在整个范围内略有下降。此外，NiPc/SWCNT 杂化物显示出比 CuPc/SWCNT 和 CoPc/SWCNT 杂化物更高的电导率。拉曼分析和能级测量表明 MPc 和 SWCNT 之间发生强烈的供体-受体相互作用。这种相互作用可能会促进界面处的载流子传输，从而增加载流子迁移率导致电导率的提高大大超出了混合规则。此外，在三种杂化物中，NiPc/SWNT 杂化物的界面能垒最低，这也有助于高导电性。最后，NiPc/SWCNT 杂化材料的最大电导率和热电功率因数分别高达 540 S cm ^-1和 120 μWm ^-1 K ^-2 ，比 CuPc/SWCNT 和 CoPc/SWCNT 高 30-50%杂化和基于金属有机小分子的 TE 材料的最佳水平。