The attractive capability of thermoelectric (TE) materials in actualizing the conversion between temperature gradient and electrical power makes them strong candidates for waste-heat recovery as well as solid-state refrigeration ^[1][2][3][1,2,3]. The practical and widespread application of TE technology strongly relies on the development of high-performance TE materials, where the TE performance of materials is evaluated by a dimensionless figure of merit, zT = α²σT/κ. The TE parameters α and σ are the Seebeck coefficient and electrical conductivity which, respectively, constitute the power factor, PF = α²σ, used to evaluate electrical conductivity characteristics. Parameter T is the Kelvin thermodynamic temperature, while κ refers to the total thermal conductivity, which is composed of two major contributions from the charge carriers (κ_E) and the lattice (κ_L), respectively. From a computational perspective, the most ideal high-performance TE material should have a large α, high σ as well as a low κ value. What cannot be avoided is the strong coupling between thermoelectric parameters regarding carrier concentration, such as when a high σ means low α and a high κ_E, limiting the improvement of zT ^[4][5][6][4,5,6]. In order to achieve high zT in traditional or emerging TE materials, various methods and approaches have been adopted to reduce the correlation between thermal and electrical properties ^[7][8][9][7,8,9], including defect engineering, size effects, alloying effect and high-entropy engineering, etc. In addition to achieving high performance, the exploration of alternative materials consists of earth-abundant and eco-friendly components to meet the sake of clean and environmental protection is also considered as one of the most popular approaches in TE field ^{[10][11][12][13]}[10,11,12,13]. In recent years, diverse bulk TE materials have been widely researched, including liquid-like Cu₂(S, Se, Te), silver-based chalcogenides, Sn(Te, S, Se), half-heuslers, etc. ^[14][15][16][14,15,16].

As an environmentally friendly and promising TE material without precious elements, the performance advantages of copper-based diamond-like TE compounds lie in their high Seebeck coefficient and low thermal conductivity ^{[17][18][19][20][21]}[17,18,19,20,21]. Typical compounds include: Cu₃SbSe₄, with a high zT of 0.89 at 650 K [19]; Cu₂SnSe₃, with α of ~250 μV·K⁻¹ in the temperature range of 300–700 K [22]; and CuInTe₂, with a κ_L value as low as 0.3 W·m⁻¹·K⁻¹ [23], etc. Copper-based diamond-like TE compounds are a type of material that conforms to the concept of “phonon-glass electron-crystal” (PGEC) [17] materials, and their crystal structures are usually composed of two sublattices ^[23][24][25][23,24,25], in which one sublattice constitutes a conductive network, while the other acts as a thermal barrier and is sometimes also known as a charge reservoir. In 2011, Skoug et al. [24] summarized the significance of lone-pair electrons in the Cu-Sb-Se diamond-like system and demonstrated that the low intrinsic κ_L in compounds came from the interaction of lone-pair electrons with neighboring atoms. Moreover, Skoug et al. [25] also confirmed that the dominant Cu-Se network controlled the electric transport while the Sn orbitals only compensated the system for electrons. Several diamond-like crystal structures evolved from thecubic zincblende structure. Simultaneously, a series of advanced CBDL compounds have been discovered since 2009, most of which have presented outstanding TE properties. The timeline of maximum zTs and the temperature dependence of zTs for selected CBDL compounds. Taking the typical diamond-like compounds of Cu(In, Ga)Te₂, Cu₃SbSe₄, and Cu₂SnSe₃ as examples, long-term efforts have shown that they all apparently have superior TE transport properties with high zTs that exceed one. For instance, Liu et al. [23] devised a pseudocubic crystal structure in CuInTe₂ compounds; thus the highest zT of 1.24 was obtained in Ag-doped CuInTe₂ compounds. A peak zT of 1.14 was attained in a Cu₂Sn_0.90In_0.10Se₃ compound at 850 K by replacing Sn sites with In. It is also worth noting that a high average zT (zT_ave)_大道） value is值对于整体 desirable for overall TE conversion efficiency. For instance, a high TE 转换效率是理想的。例如，高zT_.max在 of 1.67 at 873 K, and a 1 K 时为 67.873，并且zT_ave大道的 of 0.73, were realized in Cu，以铜为单位实现_0.7Ag银_0.3Ga加语_0.4In在_0.6Te特₂ ^[26]. In the latest research of Zhou’s group ^[27][28], record-high [26]周氏课题组最新研究[27，28]创历史新高zT_ave values_大道铜中的值分别为 of 0.73 and和 0.77 were achieved in Cu₃SbSe锑硒₄–based and Cu-基和铜₃SbS₄–based materials, respectively, which were also comparable to other state-of-the-art 分别基于材料，也可与其他最先进的TE compounds. Hence one can see that CBDL compounds are expected to become environmentally friendly candidates for TE applications and to achieve excellent performances.化合物相媲美。因此，人们可以看到CBDL化合物有望成为TE应用的环保候选者，并实现优异的性能。

2. Copper-Based Diamond-like Thermoelectric Compounds铜基类金刚石热电化合物

Copper-based diamond-like compounds (CBDL) compounds contain a large number of family members, which include ternary I–III–化合物含有大量的家族成员，包括三元I-III-VI₂ chalcopyrites, 黄胆石，I₃–V–VI₄ stannites, I斯坦尼特，我₂–IV–VI-四至六₃ stannites, quaternary 锡，第四纪I₂–II–IV–VI-二-四-六₄ compounds, and even large-cell Cu10化合物，甚至大细胞铜₁₀B₂C₄D13 tetrahedrites and Cu₁₃四面体和铜₂₆P₂Q₆S₃₂ colusites. The TE properties of selected typical 鞘石。所选典型CBDL compounds including 化合物的TE特性，包括zT_ave, _大道,zT_.max, ,α²σ, ,κ_L, and carrier concentration (n) at room temperature.和室温下的载流子浓度（N）。 Among 在CBDL compounds, CuGaTe化合物中，铜加特₂ and 和CuInTe₂ are typical 是典型的Cu–III–-III-VI₂ (（III = In, Ga; 在，GA;VI = Se, S, Te) chalcopyrites structural compounds which have exhibited excellent thermoelectric properties at higher temperatures. In 2012, ， S， Te） 黄铜矿结构化合物，在较高温度下表现出优异的热电性能。2012年，Plirdpring et al. ^[29] achieved a record zT of 1.4 in 等人[29]在CuGaTe中取得了创纪录的1.4 zT。₂ compound at 化合物在950 K, which indicated that it was a potential material in the field of TE applications. Comparatively, it was found that Cu，这表明它是TE应用领域的潜在材料。相比之下，发现CuInTe是₂在1 possessed a high zT of K时拥有18.18 at 850 K ^[20]. 850的高zT[20]。在接下来的几年中，进行了大量研究以优化黄铜矿基材料的TE输运行为。通过缺陷工程，贝聿铭的团队在A large number of studies were conducted to optimize the TE transport behaviors of chalcopyrite-based materials in the following years. Through defect engineering, Pei’s team obtained a maximum 掺杂CuGaTe中获得了1 K时的最大zT of 1为0.0 at 750 K in the Ag-doped CuGaTe₂ compound ^[30] and identified that vacancy scattering was an active approach to improve 化合物[40]并确定空位分散是改善TE transport behaviors ^[31]. Zhang et al. ^[26] synthesized a quinary alloy compound 运输行为的积极方法[80]。张等[26]合成了一种五元合金化合物Cu_0.7Ag银_0.3Ga加语_0.4In在_0.6特₂具有复杂的纳米应变域结构，具有优异的Te₂E性能，在1 with a complex nanosiK时峰值zed strain domain structure, which presented excellent TE properties with a peak zT of 1.T为64 at .873 K and an average ，平均zT为<>.<> (zT_ave)_大道） of的 0.73. Through compositing Ti。通过合成 TiO₂ nanofibers, 纳米纤维，Yang 等人[36]在CuInTet中在1 al. ^[32] achieved a maximum zT of 1.K时实现了47 at .823 K in a CuInTe的最大zT。₂–based 基于TE compound. Moreover, Chen et al. ^[23] obtained a maxim化合物。此外，Chen等人[23]在Cum zT of 1.24 in the Cu_0.75Ag银_0.2InTe英特₂ compound. The above shows that 复合。以上显示Cu(In, Ga)（In，Ga）Te。₂ diamond-like 类金刚石TE materials have a higher 材料具有更高的zTs, comparable to other advanced thermoelectric materials such as ，可与其他先进的热电材料（如PbTe ^{[33][34][35][36]} and [81，82，83，84]和SnTe ^[37][38][39]. In addition, a natural chalcopyrite mineral, [85，86，87]）相媲美。此外，天然黄铜矿矿物CuFeS₂ ^{[40][41][42][43]}, was also recognized as an advanced [52，53，54，55]，也被公认为先进的CBDL thermoelectric material. It is noteworthy that the CuFeS热电材料。值得注意的是，铜铁矿石₂ compound is a rare typical n-type TE compound among 化合物是CBDL thermoelectric materials ^[44][45].热电材料中罕见的典型n型TE化合物[88，89]。 Cu铜₃–V–VI₄ (（V = Sb, P, As; ， P， As;VI = Se, S, Te) compounds with a tetragonal diamond-like crystal structure can be approximately regarded as the superposition of four equivalent zincblendes, wherein 、S、Te）化合物具有四方金刚石样晶体结构，可近似地视为四种等效的锌混合物的叠加，其中Cu₃SbSe锑硒₄ is considered as a promising 被认为是有前途的TE candidate owing to its narrow band gap of 候选者，因为它的窄带隙为~0.3 eV ^{[19][27][46][47]}. For improving the [19，27，47，90]。用于提高铜的TE performance of Cu性能₃SbSe锑硒₄–based materials, 基于材料，Li et al. ^[48] coordinately regulated electrical and thermal transport behaviors through the incorporation of 等人[45]通过结合Sn-doping and 掺杂和AgSb来协调调节电和热传输行为_0.98Ge通用 电气_0.02Se硒₂ inclusion, and the highest zT of 1.23 was eventually achieved at 675 K. Bo et al. ^[47] s等人[1]成功地应用构型熵的概念优化了Cuccessfully applied the concept of configuration entropy to optimize the 的TE performance of Cu性能。₃SbSe锑硒₄, and the ，并且随着熵的增加，zT increased by about four times, compared to the initial phase, with the increase of entropy. In their latest report, 比初始阶段增加了约四倍。在他们的最新报告中，Zhou’s的小组[27]获得了优越的平均功率因数（聚苯乙烯_大道） group的 ^[27] attained a superior average power factor (PF_ave) of 19 µμW·cm⁻¹·K⁻² in 在300–723 K by using a small amount of foreign Al atoms as “stabilizers” to supply the high hole concentration, with almost no effect on carrier mobility. Consequently, combined with the reduced -723 K中，通过使用少量外来Al原子作为“稳定剂”来提供高空穴浓度，对载流子迁移率几乎没有影响。因此，结合降低的κ, a record-high ，创纪录的zT of 为1.4 and a 和zT_ave大道的 of 0.72 were obtained within the Cu在铜内获得₃SbSe锑硒₄–based compounds. A new unconventional doping process that can coordinate the 基于化合物。还介绍了一种可以协调材料TE properties of materials was also presented. Apart from Cu性能的新型非常规掺杂工艺。除了铜₃SbSe锑硒₄, Cu铜₃SbS₄ is also a promising Cu也是一个有前途的铜₃–V–VI₄–type of TE材料的类型[28，50，51]，并且已经证明其聚苯乙烯_大道最高可达 material ^[28][49][50], and it has been demonstrated that its PF_ave can reach up to 16.1 µμW·cm⁻¹·K⁻² and the 和zT_ave大道通过其优化，在 up0 to 0.77 between 400 and 773 K via its optimization ^[28].和 77 K 之间高达 400.773 [28]。 Different from 不同于Cu–III–-III-VI₂ and Cu和铜₃–V–VI₄ compounds, ternary Cu化合物，三元铜₂–IV–VI-四至六₃ (（IV = Sn, Ge, Pb; 锡、锇、铅;VI = Se, Te, S) compounds crystallize in more distorted structures that are far from tetragonal. Cu，Te，S）化合物结晶在远离四方的更扭曲的结构中。铜₂SnSe硒₃ is a kind of 是一种具有多种结构相的CBDL compo化合物，已被成功发现和合成，包括立方相、四方相、正交相和单斜相，涉及22种变体[62]。Hund with diverse structural phases, which has been found and synthesized successfully, includinget al. [<>] in改进了 cubic, tetragonal, orthogonal, and monoclinic phases involving three variants ^[22]. Hu et al. ^[51] improved the Cu 的 TE transport behaviors of Cu传输行为₂SnSe硒₃ by enhancin通过Mg the crystal symmetry of it via Mg-doping and intensifying the phonon scattering thro掺杂增强其晶体对称性，并通过引入位错和纳米沉淀物来增强声子散射。同样，Ming等人[65]在Cugh the introduction of dislocations and nanoprecipitates. Similarly, Ming et al. ^[52] obtained a peak zT of 1 K处获得了51.51 at 858 K in the Cu的峰值zT。₂Sn锡_0.82In在_0.18Se硒_2.7S_0.3 compo通过调节带状结构和引入多尺度缺陷进行复合。此外，秦等人[1]通过构建固有点缺陷（包括高密度堆积断层和内生长纳米针）来阻碍Cund through regulating the band structure and introducing multi-scale defects. In addition, a record-high zT of 1.中的中频和低频声子，从而在61 was obtained at 848 K处获得了创纪录的848.66 by Qin et al. ^[53] by constructing the intrinsic point defects, including high-dense stacking faults and endo-grown nanoneedles, to obstruct mid- as well as low-frequency phonons in CuzT。₂SnSe硒₃ compounds. Except for Cu化合物。除铜₂SnSe硒₃, Cu铜₅A一个₂B₇ (（A = Si, Ge, Sn; B = S, Se, Te), with a centrosymmetric space group 硅、锗、锡;B = S，Se，Te），具有中心对称空间群C2/m, is also a kind of distorted ，也是一种扭曲的CBDL compound which has been considered to possess a non-centrosymmetric cubic structure, with the phase crystallized as C-centered ^[54][55][56]. An undesirable characteristic of Cu化合物，被认为具有非中心对称立方结构，相结晶为C中心[91，92，93]。铜的不良特性₅A一个₂B₇ compounds is that they represent metal-like behaviors, such as the carrier concentration and κ of 化合物是它们代表类似金属的行为，例如Cu的载流子浓度和κ₅Sn锡₂Te特₇在 at 300 K are 1.39×时是 1.39 × 10²¹ cm厘米⁻³和 and 15.1 W·m⁻¹·K⁻¹, respectively ^[55]. Simultaneously, zinc atoms have been proven to be effective dopants for strengthening the semiconductor properties of Cu，分别[92]。同时，锌原子已被证明是增强铜的半导体性能的有效掺杂剂₅Sn锡₂Te特₇ compounds化合物; Sturm et al. ^[56] introduced a zinc dopant into CuSturm等人[93]将锌掺杂剂引入铜₅Sn锡₂Se硒₇ and Cu和铜₅Sn锡₂Te特₇ compounds, which also supports this conclusion. Especially noteworthy is that the effect of zinc doping is not optimal, and the 化合物，这也支持了这一结论。特别值得注意的是，锌掺杂的效果并不理想，化合物的TE performance of the compound still needs further improvement.性能仍有待进一步提高。 Quaternary Cu第四纪铜₂–II–IV–VI-二-四-六₄ (（II = Co, Mn, Hg, Mg, Zn, Cd, Fe; IV = Sn, Ge; 钴、锰、汞、镁、锌、镉、铁;IV = 锡，锗;VI = Se, S, Te) compounds with more complex tetragonal structures have also been widely studied. The distinguishing features of quaternary CBDL compounds are they possess a wider bandgap and a relatively lower carrier mobility compared with the ternary CBDL compounds ^{[57][58][59][60][61][62][63][64][65]}. Taking the orthorhombic enargite-type Cu，S，Te）具有更复杂的四方结构的化合物也得到了广泛的研究。与三元CBDL化合物相比，季CBDL化合物的显著特征是它们具有更宽的带隙和相对较低的载流子迁移率[68，70，76，94，95，96，97，98，99]。取斜方晶石型铜₂MnGeS锰基镉₄ as an example ^[61], the bandgap of it is 例如[95]，它的带隙在初始阶段为~1.0 eV in the initial phase while it only converts to ，而在Cu中仅转换为0.9 eV in the Cu_2.5Mn锰_0.5GeS₄ by adjusting the ratio of 通过调整Mn and Cu atoms. The large-cell Cu和Cu原子的比例。大细胞铜₁₀B₂C₄D₁₃ ^{[66][67][68][69]} [100，101，102，103] (（B = Ag, Cu; C = Co, Ni, Zn, Cu, Mn, Fe, Hg, Cd; 银，铜;C = 钴、镍、锌、铜、锰、铁、汞、镉;Q = Sb, Bi, As; ， Bi， As;Q = Se, S) tetrahedrites have even more complex crystal structures. The featured， S）四面体具有更复杂的晶体结构。特色的“PGEC” framework is also displayed in the 框架也显示在Cu₁₂Sb某人₄S₁₃ tetrahedrite, where the electric transmission is controlled by a 四面体，其中电传输由CuS控制₄ network and the thermal transmission is governed by a cavity polyhedral consisting of 网络和热传递由由CuS组成的空腔多面体控制₃和 and SbS₃组 groups ^[66]. In [100]。2013, 年，Lu等人[102]在铜中0 et al. ^[68] achieved an enhanced zT of 0.K时实现了95 at .720 K in Cu的增强zT。₁₂Sb某人₄S₁₃ utilizing Zn-doping. Moreover, 利用锌掺杂。此外，Li等人[103]在多孔Cu中在1 et al. ^[69] attained a high zT of K处获得了15.15 at 723 K in a porous Cu723的高zT。₁₂Sb某人₄S₁₃–based material基于材料; a segmented single-leg device based on the material was successfully fabricated which realized a high conversion efficiency of 6% when the 成功制备了基于该材料的分段单支腿装置，当ΔT达到6 reached up to 419 K. CuK时，实现了419%的高转换效率。₂₆P₂Q₆S₃₂ ^{[70][71][72][73][74]}([104，105，106，107，108] （P = V,， Ta, Nb, W, Mo; ， Nb， W， Mo;Q = Ge, Sn, As, Sb) colusites are other large-cell examples, which possess 66 atoms in a crystal cell while the tetrahedrites possess 58 atoms. Therefore, the common characteristic of both is their inherent low ，Sn，As，Sb）镭石是其他大细胞的例子，它们在一个晶体细胞中拥有66个原子，而四面体具有58个原子。因此，两者的共同特征是它们固有的低κ derived from high structural inhomogeneity ^[74][75]. For instance, 源于高结构不均匀性[108，109]。例如，Guilmeau’s group ^[71] obtained the lowest κ of 的群[105]获得了0.4 W·m的最低κ。⁻¹·K⁻¹ at在铜中的 300 K in the Cu₂₆V₂Sn锡₆S₃₂ colusite, which was attributed to the structural complexity of colusite and mass fluctuations among the 鞘钝石，归因于鞘钝石的结构复杂性和Cu, V and Sn atoms. In 2018, they further elucidated the potential mechanism related to the fountainhead of intrinsically low 、V和Sn原子之间的质量波动。2018年，他们进一步阐明了与钝体固有低κ for a colusite along with the influence of antisite defects and 源头相关的潜在机制，以及反位点缺陷和S-vacancies on carrier concentration ^[71][72].空位对载流子浓度的影响[105，106]。