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In the thermoelectric field, GeSe is a two-dimensional layered semiconductor with a large band gap, intrinsically low carrier concentration and poor thermoelectric figure of merit ZT. In this work, a series of GeSe1–xTex (x = 0, 0.05, 0.15, 0.25, 0.35, 0.45) polycrystalline samples is prepared by melting and quenching combined with spark plasma activation sintering process. The influences of Te content on the phase structure and thermoelectric transport properties of GeSe are systematically studied. The results indicate that with the increase of Te content, the crystal structure of GeSe gradually changes from orthorhombic to rhombohedral structure. This reduces the band gap of the material, and simultaneously increases the carrier concentration and mobility. Meanwhile, the energy band degeneracy of the compound increases significantly because of enhanced crystal symmetry in this process, thereby considerably improving the effective mass of carriers. Altogether, the power factor of the rhombohedral GeSe is increased by about 2 to 3 orders of magnitude compared with that of the orthorhombic phase GeSe. In addition, the rhombohedral phase GeSe has abundant cationic vacancy defects and softened phonons arising from its ferroelectric feature, leading the lattice thermal conductivity to be 60% lower than orthorhombic one. The GeSe0.55Te0.45 sample achieves a peak ZT of 0.75 at 573 K, which is 19 times that of pristine GeSe. Crystal structure engineering could be considered as an effective way of improving the thermoelectric performance of GeSe compounds.
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Keywords:
- GeSe /
- crystal structure engineering /
- thermoelectric properties /
- semiconductors
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Google Scholar
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图 1 (a)室温下正交相GeSe的晶体结构; (b)~900 K 正交结构GeSe相变为立方结构
Figure 1. (a) Crystal structure of orthorhombic GeSe at 300 K and its evolution with temperature; (b) phase transition to cubic one occurring around 900 K.
图 2 GeSe1–xTex (x = 0—0.45)样品的 (a)粉末XRD图谱; (b) 28°—35°粉末XRD图谱; (c)晶胞参数; (d) GeSe-GeTe赝二元相图
Figure 2. (a) Powder XRD patterns of GeSe1–xTex samples (x = 0–0.45); (b) enlarged view of XRD patterns (2θ = 28°–35°); (c) the a, b and c lattice parameters of GeSe1–xTex samples (x = 0–0.45); (d) GeSe-GeTe pseudo-binary phase diagram.
图 3 GeSe1–xTex(x = 0—0.45)样品末XRD精修图谱与实测图谱: (a) x = 0.15; (b) x = 0.25; (c) x = 0.35
Figure 3. Rietveld refinement XRD results of GeSe1–xTex
(x = 0–0.45): (a) x = 0.15; (b) x = 0.25; (c) x = 0.35. 
图 4 GeSe1–xTex (x = 0—0.45)化合物的断面FESEM图片 (a) x = 0; (b) x = 0.05; (c) x = 0.15; (d) x = 0.25; (e) x = 0.35; (f) x = 0.45
Figure 4. FESEM images of the freshly fractured surface of GeSe1–xTex (x = 0–0.45): (a) x = 0; (b) x = 0.05; (c) x = 0.15; (d) x = 0.25; (e) x = 0.35; (f) x = 0.45.
图 5 GeSe1–xTex样品的背散射电子像和对应元素的面分布图谱 (a)—(d) x = 0.05; (e)—(h) x = 0.45; (i)—(l) x = 0.15; (m)—(p) x = 0.35
Figure 5. Back-scattered electron (BSE) images and corresponding elemental distribution mappings of GeSe1–xTex samples: (a)–(d) x = 0.05; (e)–(h) x = 0.45; (i)–(l) x = 0.15; (m)–(p) x = 0.35.
图 6 GeSe1–xTex(x = 0—0.45)样品的电输运性质随温度变化曲线: (a) Seebeck系数, 插图为x = 0与x = 0.05样品; (b)电导率, 插图为x = 0与x = 0.05样品
Figure 6. Temperature dependence of (a) Seebeck coefficient and (b) electrical conductivity for GeSe1–xTex (x = 0–0.45) samples. Insets are enlarged views for x = 0 and x = 0.05 samples.
图 7 室温下GeSe1–xTex(x = 0—0.45)样品的(a)载流子浓度(pH)和(b)迁移率(µH)
Figure 7. Room temperature (a) carrier concentration (pH) and (b) carrier mobility (µH) versus Te content (x) in GeSe1–xTex (x = 0–0.45) samples.
图 8 GeSe1–xTex (x = 0—0.45)样品: (a)室温下的Pisarenko曲线和(b)功率因子随温度变化曲线
Figure 8. (a) Pisarenko curves at room temperature and (b) temperature dependent power factors of GeSe1–xTex samples.
图 9 GeSe1–xTex (x = 0—0.45)样品的(a)总热导率和(b)晶格热导率随温度变化曲线
Figure 9. Temperature dependence of (a) total and (b) lattice thermal conductivities of GeSe1–xTex (x = 0–0.45) samples.
图 10 GeSe1–xTex 样品的DSC曲线 (a) x = 0.05; (b) x = 0.15; (c) x = 0.35; (d) x = 0.45
Figure 10. DSC curves of GeSe1–xTex samples: (a) x = 0.05, (b) x = 0.15, (c) x = 0.35, (d) x = 0.45.
图 11 GeSe1–xTex(x = 0—0.45)样品的ZT值随温度变化的关系曲线
Figure 11. Temperature dependence of ZT values of GeSe1–xTex (x = 0–0.45) samples.
表 1 室温下GeSe1–xTex样品中各种物相的质量分数
Table 1. Mass fractions of various phases in GeSe1–xTex (x = 0.15, 0.25, 0.35) samples at room temperature.
样品组分(GeSe1–xTex) 质量分数/% 正交相 菱方相 x = 0.15 80.9 19.1 x = 0.25 58.5 41.5 x = 0.35 11.2 88.8 
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[1] Wang Y, Shi Y, Mei D, Chen Z 2017 Appl. Energy 205 710
Google Scholar
[2] Kim Y J, Gu H M, Kim C S, Choi H, Lee G, Kim S, Yi K K, Lee S G, Cho B J 2018 Energy 162 526
Google Scholar
[3] Tan G, Zhao L D, Kanatzidis M G 2016 Chem. Rev. 116 12123
Google Scholar
[4] Okazaki A 1958 J. Phys. Soc. Jpn. 13 1151
Google Scholar
[5] Sist M, Gatti C, Norby P, Cenedese S, Kasai H, Kato K, Iversen B B 2017 Chem. Eur. J. 23 6888
Google Scholar
[6] Kim Y, Choi I-H 2018 J. Korean Phys. Soc. 72 238
Google Scholar
[7] Hao S, Shi F, Dravid V P, Kanatzidis M G, Wolverton C 2016 Chem. Mater. 28 3218
Google Scholar
[8] Fan Q, Yang J, Cao J, Liu C 2021 R. Soc. Open Sci. 8 201980
Google Scholar
[9] Yuan K, Sun Z, Zhang X, Tang D 2019 Sci. Rep. 9 9490
Google Scholar
[10] Roychowdhury S, Ghosh T, Arora R, Waghmare U V, Biswas K 2018 Angew. Chem. Int. Ed. 57 15167
Google Scholar
[11] Yan M, Geng H, Jiang P, Bao X 2020 J. Energy Chem. 45 83
Google Scholar
[12] Zhang X, Shen J, Lin S, Li J, Chen Z, Li W, Pei Y 2016 J. Materiomics 2 331
Google Scholar
[13] Huang Z, Miller S A, Ge B, Yan M, Anand S, Wu T, Nan P, Zhu Y, Zhuang W, Snyder G J, Jiang P, Bao X 2017 Angew. Chem. Int. Ed. 56 14113
Google Scholar
[14] Yan M, Tan X, Huang Z, Liu G, Jiang P, Bao X 2018 J. Mater. Chem. A 6 8215
Google Scholar
[15] Sarkar D, Ghosh T, Roychowdhury S, Arora R, Sajan S, Sheet G, Waghmare U V, Biswas K 2020 J. Am. Chem. Soc. 142 12237
Google Scholar
[16] Li J, Zhang X, Lin S, Chen Z, Pei Y 2017 Chem. Mater. 29 605
Google Scholar
[17] Wang Z, Wu H, Xi M, Zhu H, Dai L, Xiong Q, Wang G, Han G, Lu X, Zhou X, Wang G 2020 ACS Appl. Mater. Interfaces 12 41381
Google Scholar
[18] Sidharth D, Alagar Nedunchezhian A S, Akilan R, Srivastava A, Srinivasan B, Immanuel P, Rajkumar R, Yalini Devi N, Arivanandhan M, Liu C J, Anbalagan G, Shankar R, Jayavel R 2021 Sustain. Energy Fuels 5 1734
Google Scholar
[19] Shaabani L, Aminorroaya-Yamini S, Byrnes J, Akbar Nezhad A, Blake G R 2017 ACS Omega 2 9192
Google Scholar
[20] 范人杰, 江先燕, 陶奇睿, 梅期才, 唐颖菲, 陈志权, 苏贤礼, 唐新峰 2021 70 137102
Google Scholar
Fan R J, Jiang X Y, Tao Q R, Mei Q C, Tang Y F, Chen Z Q, Su X L, Tang X F 2021 Acta Phys. Sin. 70 137102
Google Scholar
[21] Cao Y, Su X, Meng F, Bailey T P, Zhao J, Xie H, He J, Uher C, Tang X 2020 Adv. Funct. Mater. 30 2005861
Google Scholar
[22] 黄平, 游理, 梁星, 张继业, 骆军 2019 68 077201
Google Scholar
Huang P, You L, Liang X, Zhang J Y, Luo J 2019 Acta Phys. Sin. 68 077201
Google Scholar
[23] 苏贤礼, 唐新峰, 李涵, 邓书康 2008 57 6488
Google Scholar
Su X L, Tang X F, Li H, Deng S G 2008 Acta Phys. Sin. 57 6488
Google Scholar
[24] Sun J, Su X, Yan Y, Liu W, Tan G, Tang X 2020 ACS Appl. Energy Mater. 3 2
Google Scholar
[25] Zhang W, Chen C, Yao H, Xue W, Li S, Bai F, Huang Y, Li X, Lin X, Cao F, Sui J, Wang S, Yu B, Wang Y, Liu X, Zhang Q 2020 Chem. Mater. 32 6983
Google Scholar
[26] Nshimyimana E, Hao S, Su X, Zhang C, Liu W, Yan Y, Uher C, Wolverton C, Kanatzidis M G, Tang X 2020 J. Mater. Chem. A 8 1193
Google Scholar
[27] Zheng Z, Su X, Deng R, Stoumpos C, Xie H, Liu W, Yan Y, Hao S, Uher C, Wolverton C, Kanatzidis M G, Tang X 2018 J. Am. Chem. Soc. 140 2673
Google Scholar
[28] Chen S, Bai H, Li J, Pan W, Jiang X, Li Z, Chen Z, Yan Y, Su X, Wu J, Uher C, Tang X 2020 ACS Appl. Mater. Interfaces 12 19664
Google Scholar
[29] Franz R, Wiedemann G 1853 Ann. Phys. 165 497
[30] Pietrak K, Wisniewski T S 2015 J. Power Technol. 95 14
[31] Banik A, Ghosh T, Arora R, Dutta M, Pandey J, Acharya S, Soni A, Waghmare U V, Biswas K 2019 Energy Environ. Sci. 12 589
Google Scholar
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