Crystal Growth and Thermoelectric Properties of Zintl Phase Mg3X2 (X=Sb, Bi) Based Materials: a Review

doi:10.15541/jim20220356

Abstract

Abstract:

Zintl phase Mg₃X₂ (X=Sb, Bi) based thermoelectric materials have attracted much attention because of their non-toxic, low cost and high performance. Compared with polycrystalline materials, the Mg₃X₂ crystals are of great value in revealing material’s intrinsic and anisotropic thermoelectric properties, as well as providing effective strategies for enhancing electrical and thermal transport properties. Therefore, the recent progress of single crystal growth and thermoelectric properties for Mg₃X₂ crystals are systematically summarizes in this paper. Due to the volatility and causticity of Mg element, several different methods such as slow cooling method, directional solidification method, flux method, and flux Bridgman method are widely used for synthesizing Mg₃X₂ crystals, in which the flux Bridgman method is more competitive to prepare large size bulk crystals. Researchers found that both n-type and p-type Mg₃Sb₂ crystals show an anisotropy thermoelectric transport property. The crystal growth rate, the concentration of self-doped Mg element, the concentration of impurity doping or alloying elements have a great impact on both electrical and thermal transport properties for Mg₃Sb₂ crystals. So far, the p-type and n-type Mg₃Sb₂ crystals with ZT value of 0.68 and 0.82 are achieved, respectively. This paper reviews the recent progress of growth and thermoelectrics properties of Zintl phase Mg₃X₂-based crystals, revealing that the flux Bridgman method is the most effective method to produce large-sized Mg₃X₂-based crystals. Tuning chemical composition of Mg₃X₂-based crystal by doping and forming solid solution for optimal carrier concentration and band structure engineering is expected to further improve the thermoelectric performance of Mg₃X₂-based crystal. The above-mentioned growth method and research strategies provide a significant guidance for the in-depth understanding of the Mg₃X₂-based crystal in the future.

Key words: Zintl phase, Mg₃X₂, crystal growth, thermoelectric property, review

CLC Number:

TQ174

LIN Siqi, LI Airan, FU Chenguang, LI Rongbing, JIN Min. Crystal Growth and Thermoelectric Properties of Zintl Phase Mg₃X₂ (X=Sb, Bi) Based Materials: a Review[J]. Journal of Inorganic Materials, 2023, 38(3): 270-279.

Figures/Tables 8

Fig. 1 Crystal structure of Mg3X2 (X=Sb, Bi)[33]

Fig. 2 Phase diagram of Mg3X2 compounds[46-47] (a) Mg-Sb and (b) Mg-Bi binary phase diagram

Fig. 3 MgSb2 crystals grown by slow cooling method (a) XRD patterns of Mg3-xMnxSb2 crystal powder grown by slow cooling method; (b) XRD patterns of (001) cleavage plane; (c) Morphology of as grown Mg3-xMnxSb2 crystal; (d) SEM image of cleavage plane[48]; (e) Ag-doped Mg3Sb2 crystal grown by modified slow cooling method[50]

Fig. 4 MgSb2 crystals grown by directional solidification method[51] (a) Ag-doped Mg3Sb2 crystal growth diagram; (b) The as-grown crystal1. The graphite; 2. Raw materials; 3. Melting zone; 4. Graphite heater; 5. Induction coil; 6. Boron nitride baffle; 7. Solidified crystal; 8. Seed crystal

Fig. 5 Mg3Sb2-xBix crystals grown by flux method (a) Sb flux grown Mg3Sb2[53]; (b) Te-doped Mg3Sb2 crystals[54]; (c) Mg flux grown Mg3Bi1.25Sb0.75 crystal[55]

Fig. 6 MgSb2 crystal grown by flux method[56] (a) Schematic diagram of Y-doped Mg3Sb2 crystal growth by flux Bridgman method; (b) As grown crystal; (c) Mg3Sb2 single crystal with the size of 8 mm×10 mm×25 mm

Fig. 7 Thermoelectric properties of Mg3Sb2-xBix crystals (a) Thermoelectric properties of Mg3Sb2 crystals grown by modified temperature cooling method[50]; (b) Sb/Bi flux Bridgman method[56]; (c) Directional solidification method[51]; (d) Sb flux method[54]; (e) Mg flux method[55]

Table 1 Growth results of Mg3X2 crystal by different methods and their thermoelectric properties

Method	Composition	Type	Shape and size	ZT_max	Year	Ref.
Temperature cooling	Mn-doped Mg₃Sb₂	n	Flake, 6-7 mm	0.11 (//ab plane, 500 K)	2014	[48]
	Mg₃Sb_2-_xBi_x	p	Flake, 6-7 mm	0.006 (//ab plane, 300 K)	2015	[49]
	Ag-doped Mg₃Sb₂	p	Bulk, 3 mm×6 mm×10 mm	0.03 (//ab plane, 300 K) 0.12 (┴ab plane, 300 K)	2021	[50]
Flux method	Mg₃Sb₂ (Sb Flux)	p	Flake, 6-7 mm	-	2018	[53]
	Mg₃Bi₂ (Bi Flux)	p	Flake, 6-7 mm	-	2018	[53]
	Y-doped Mg₃Sb₂(Mg Flux)	n	Flake, 3-8 mm	-	2020	[55]
	Y-doped Mg₃Bi₂(Mg Flux)	n/p	Flake, 3-8 mm	-	2020	[55]
	Y-doped Mg₃Bi_1.25Sb_0.75(Mg Flux)	n	Flake, 3-10 mm	0.82 (//ab plane, 325 K)	2020	[55]
	Te-doped Mg₃Sb₂ (Sb Flux)	n	Flake, 5-10 mm	0.78 (//ab plane, 600 K)	2020	[54]
Directional solidification	Ag-doped Mg₃Sb₂	p	Ingot, ϕ 10 mm×50 mm	0.62 (//ab plane, 800 K) 0.68 (┴ab plane, 800 K)	2020	[51]
Flux Bridgman	Y-doped Mg₃Sb₂(Sb/Bi Flux)	n	Bulk, 8 mm×10 mm×25 mm	0.60 (//ab plane, 700 K) 0.48 (┴ab plane, 700 K)	2021	[56]

References 58

[1]	BELL L E. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science, 2008, 321(5895): 1457. DOI PMID
[2]	SHI X, CHEN L, UHER C. Recent advances in high-performance bulk thermoelectric materials. International Materials Reviews, 2016, 61(6): 379. DOI URL
[3]	GAYNER C, KAR K K. Recent advances in thermoelectric materials. Progress in Materials Science, 2016, 83: 330. DOI URL
[4]	HE J, TRITT T M. Advances in thermoelectric materials research: looking back and moving forward. Science, 2017, 357(6358): eaak9997. DOI URL
[5]	IOFFE A F, STILBANS L S, IORDANISHVILI E K, et al. Semiconductor thermoelements and thermoelectric cooling. Physics Today, 1959, 12(5): 42.
[6]	MAO J, LIU Z, ZHOU J, et al. Advances in thermoelectrics. Advances in Physics, 2018, 67(2): 69.
[7]	WEI T R, QIN Y, DENG T, et al. Copper chalcogenide thermoelectric materials. Science China Materials, 2019, 62(1): 8. DOI
[8]	ZHAO K, QIU P, SHI X, et al. Recent advances in liquid-like thermoelectric materials. Advanced Functional Materials, 2020, 30(8): 1903867. DOI URL
[9]	SHI X L, ZOU J, CHEN Z G. Advanced thermoelectric design: from materials and structures to devices. Chemical Reviews, 2020, 120(15): 7399. DOI URL
[10]	ZHANG X, BU Z, SHI X, et al. Electronic quality factor for thermoelectrics. Science Advances, 2020, 6(46): eabc0726. DOI URL
[11]	ZHU T, LIU Y, FU C, et al. Compromise and synergy in high- efficiency thermoelectric materials. Advanced Materials, 2017, 29(14): 1605884. DOI URL
[12]	BISWAS K, HE J, BLUM I D, et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature, 2012, 489(7416): 414. DOI
[13]	PEI Y, SHI X, LALONDE A, et al. Convergence of electronic bands for high performance bulk thermoelectrics. Nature, 2011, 473(7345): 66. DOI
[14]	ZHAO L D, LO S H, ZHANG Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508(7496): 373. DOI
[15]	LIU H, SHI X, XU F, et al. Copper ion liquid-like thermoelectrics. Nature Materials, 2012, 11(5): 422. DOI PMID
[16]	HEREMANS J P, JOVOVIC V, TOBERER E S, et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008, 321(5888): 554. DOI PMID
[17]	HSU K F, LOO S, GUO F, et al. Cubic AgPb_mSbTe₂₊_m: bulk thermoelectric materials with high figure of merit. Science, 2004, 303(5659): 818. DOI URL
[18]	GUPTA R P, MCCARTY R, SHARP J. Practical contact resistance measurement method for bulk Bi₂Te₃-based thermoelectric devices. Journal of Electronic Materials, 2014, 43(6): 1608. DOI URL
[19]	PEI J, CAI B, ZHUANG H L, et al. Bi₂Te₃-based applied thermoelectric materials: research advances and new challenges. National Science Review, 2020, 7(12): 1856. DOI URL
[20]	MAO J, CHEN G, REN Z. Thermoelectric cooling materials. Nature Materials, 2021, 20(4): 454. DOI PMID
[21]	PINCHERLE L, RADCLIFFE J M. Semiconducting intermetallic compounds. Advances in Physics, 1956, 5(19): 271. DOI URL
[22]	SLACK G A. New materials and performance limits for thermoelectric cooling. CRC Handbook of Thermoelectrics, 2018: 407.
[23]	TAMAKI H, SATO H K, KANNO T. Isotropic conduction network and defect chemistry in Mg₃₊_δSb₂-based layered Zintl compounds with high thermoelectric performance. Advanced Materials, 2016, 28(46): 10182. DOI URL
[24]	MAO J, SHUAI J, SONG S, et al. Manipulation of ionized impurity scattering for achieving high thermoelectric performance in n-type Mg₃Sb₂-based materials. Proceedings of the National Academy of Sciences, 2017, 114(40): 10548. DOI URL
[25]	ZHANG J, SONG L, PEDERSEN S H, et al. Discovery of high- performance low-cost n-type Mg₃Sb₂-based thermoelectric materials with multi-valley conduction bands. Nature Communications, 2017, 8(1): 13901. DOI
[26]	KUO J J, KANG S D, IMASATO K, et al. Grain boundary dominated charge transport in Mg₃Sb₂-based compounds. Energy & Environmental Science, 2018, 11(2): 429.
[27]	IMASATO K, KANG S D, SNYDER G J. Exceptional thermoelectric performance in Mg₃Sb_0.6Bi_1.4for low-grade waste heat recovery. Energy & Environmental Science, 2019, 12(3): 965.
[28]	MAO J, ZHU H, DING Z, et al. High thermoelectric cooling performance of n-type Mg₃Bi₂- based materials. Science, 2019, 365(6452): 495. DOI URL
[29]	SHU R, ZHOU Y, WANG Q, et al. Mg₃₊_δSb_xBi_2-_x family: a promising substitute for the state-of-the-art n-type thermoelectric materials near room temperature. Advanced Functional Materials, 2019, 29(4): 1807235. DOI URL
[30]	WOOD M, KUO J J, IMASATO K, et al. Improvement of low- temperature ZT in a Mg₃Sb₂-Mg₃Bi₂ solid solution via Mg-vapor annealing. Advanced Materials, 2019, 31(35): 1902337. DOI URL
[31]	ZHANG F, CHEN C, YAO H, et al. High-performance N-type Mg₃Sb₂ towards thermoelectric application near room temperature. Advanced Functional Materials, 2020, 30(5): 1906143. DOI URL
[32]	YING P, HE R, MAO J, et al. Towards tellurium-free thermoelectric modules for power generation from low-grade heat. Nature Communications, 2021, 12(1): 1121. DOI PMID
[33]	MARTINEZ-RIPOLL M, HAASE A, BRAUER G. The crystal structure of α-Mg₃Sb₂. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 1974, 30(8): 2006. DOI URL
[34]	LI A, FU C, ZHAO X, et al. High-performance Mg₃Sb_2-_xBi_x thermoelectrics: progress and perspective. Research, 2020, 2020: 1934848.
[35]	ZHENG C, HOFFMANN R, NESPER R, et al. Site preferences and bond length differences in CaAl₂Si₂-type Zintl compounds. Journal of the American Chemical Society, 1986, 108(8): 1876. DOI URL
[36]	OHNO S, IMASATO K, ANAND S, et al. Phase boundary mapping to obtain n-type Mg₃Sb₂-based thermoelectrics. Joule, 2018, 2(1): 141. DOI URL
[37]	BHARDWAJ A, RAJPUT A, SHUKLA A K, et al. Mg₃Sb₂-based Zintl compound: a non-toxic, inexpensive and abundant thermoelectric material for power generation. RSC Advances, 2013, 3(22): 8504. DOI URL
[38]	MAO J, WU Y, SONG S, et al. Defect engineering for realizing high thermoelectric performance in n-type Mg₃Sb₂-based materials. ACS Energy Letters, 2017, 2(10): 2245. DOI URL
[39]	SHUAI J, WANG Y, KIM H S, et al. Thermoelectric properties of Na-doped Zintl compound: Mg_3-_xNa_xSb₂. Acta Materialia, 2015, 93: 187. DOI URL
[40]	ZHANG J, SONG L, SIST M, et al. Chemical bonding origin of the unexpected isotropic physical properties in thermoelectric Mg₃Sb₂ and related materials. Nature Communications, 2018, 9(1): 4716. DOI
[41]	SUN X, LI X, YANG J, et al. Achieving band convergence by tuning the bonding ionicity in n-type Mg₃Sb₂. Journal of Computational Chemistry, 2019, 40(18): 1693. DOI URL
[42]	SHI X, ZHAO T, ZHANG X, et al. Extraordinary n-type Mg₃SbBi thermoelectrics enabled by yttrium doping. Advanced Materials, 2019, 31(36): 1903387. DOI URL
[43]	ZHANG F, CHEN C, YAO H, et al. High-performance N-type Mg₃Sb₂ towards thermoelectric application near room temperature. Advanced Functional Materials, 2020, 30(5): 1906143. DOI URL
[44]	SHI X, ZHANG X, GANOSE A, et al. Compromise between band structure and phonon scattering in efficient n-Mg₃Sb_2-_xBi_x thermoelectrics. Materials Today Physics, 2021, 18: 100362. DOI URL
[45]	ZHANG J, SONG L, IVERSEN B B. Rapid one-step synthesis and compaction of high-performance n-type Mg₃Sb₂ thermoelectrics. Angewandte Chemie International Edition, 2020, 59(11): 4278. DOI URL
[46]	NAYEB-HASHEMI A A, CLARK J B. The Mg-Sb (magnesium- antimony) system. Bulletin of Alloy Phase Diagrams, 1984, 5(6): 579. DOI URL
[47]	GRUBE G. Metallographische mitteilungen aus dem institut für anorganische chemie der universität göttingen. XXV. Über die legierungen des magnesiums mit kadmium, zink, wismut und antimon. Zeitschrift für Anorganische Chemie, 1906, 49(1): 72. DOI URL
[48]	KIM S, KIM C, HONG Y K, et al. Thermoelectric properties of Mn-doped Mg-Sb single crystals. Journal of Materials Chemistry A, 2014, 2(31): 12311. DOI URL
[49]	KIM S H, KIM C M, HONG Y K, et al. Thermoelectric properties of Mg₃Sb_2-_xBi_x single crystals grown by Bridgman method. Materials Research Express, 2015, 2(5): 055903. DOI URL
[50]	LI A, HU C, HE B, et al. Demonstration of valley anisotropy utilized to enhance the thermoelectric power factor. Nature Communications, 2021, 12(1): 5408. DOI PMID
[51]	LI X, XIE H, YANG B, et al. Influence of growth rate and orientation on thermoelectric properties in Mg₃Sb₂ crystal. Journal of Materials Science: Materials in Electronics, 2020, 31(12): 9773. DOI
[52]	JIN M, YANG W H, WANG X H, et al. Growth and characterization of ZnTe single crystal via a novel Te flux vertical Bridgman method. Rare Metals, 2021, 40(4): 858. DOI
[53]	XIN J, LI G, AUFFERMANN G, et al. Growth and transport properties of Mg₃X₂ (X=Sb, Bi) single crystals. Materials Today Physics, 2018, 7: 61. DOI URL
[54]	IMASATO K, FU C, PAN Y, et al. Metallic n-type Mg₃Sb₂ single crystals demonstrate the absence of ionized impurity scattering and enhanced thermoelectric performance. Advanced Materials, 2020, 32(16): 1908218. DOI URL
[55]	PAN Y, YAO M, HONG X, et al. Mg₃(Bi, Sb)₂ single crystals towards high thermoelectric performance. Energy & Environmental Science, 2020, 13(6): 1717.
[56]	JIN M, LIN S, LI W, et al. Nearly isotropic transport properties in anisotropically structured n-type single-crystalline Mg₃Sb₂. Materials Today Physics, 2021, 21: 100508. DOI URL
[57]	JIN M, SHAO H, HU H, et al. Growth and characterization of large size undoped p-type SnSe single crystal by Horizontal Bridgman method. Journal of Alloys and Compounds, 2017, 712: 857. DOI URL
[58]	KAIBE H, TANAKA Y, SAKATA M, et al. Anisotropic galvanomagnetic and thermoelectric properties of n-type Bi₂Te₃ single crystal with the composition of a useful thermoelectric cooling material. Journal of Physics and Chemistry of Solids, 1989, 50(9): 945. DOI URL

Crystal Growth and Thermoelectric Properties of Zintl Phase Mg₃X₂ (X=Sb, Bi) Based Materials: a Review

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 58

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LI Hantao, SHEN Qiang, LUO Guoqiang, WANG Xuefei, GAO Ming, CHEN Chen. Research Progress on Structure and Performance Regulation of Silicon-based Anode Materials via Mechanical Ball Milling [J]. Journal of Inorganic Materials, 2026, 41(5): 561-572.
[2]	XIE Chenyi, MIAO Huaming, ZHANG Weiran, LIU Rongjun, WANG Yanfei, LI Duan. Research Progress on Theoretical Calculation in the Field of High-entropy Ceramics [J]. Journal of Inorganic Materials, 2026, 41(5): 545-560.
[3]	LI Xuan, YE Kuicai, FENG Jiayin, QIU Jiajun, QIAN Wenhao, XING Min. Surface Modification of Titanium-based Dental Implants for Soft Tissue Sealing: A Review [J]. Journal of Inorganic Materials, 2026, 41(4): 432-444.
[4]	PENG Dezhao, LI Rui, WANG Wenhong, WANG Zirui, ZHANG Zhizhen. Research Progress on Sodium Chloride Solid Electrolytes [J]. Journal of Inorganic Materials, 2026, 41(4): 409-420.
[5]	CHEN Kun, JIANG Yonggang, FENG Junzong, LI Liangjun, HU Yijie, FENG Jian. Research Progress on Lanthanum Zirconate Porous Materials for Thermal Insulation [J]. Journal of Inorganic Materials, 2026, 41(4): 421-431.
[6]	WEI Lianjin, QI Zhijie, WANG Xin, ZHU Junwu, FU Yongsheng. Modification of Nanodiamond and Its Application in Electrocatalytic Oxygen Reduction Reaction [J]. Journal of Inorganic Materials, 2026, 41(3): 273-288.
[7]	LIU Zhanyi, LI Mian, OUYANG Xiaoping, CHAI Zhifang, HUANG Qing. Recent Progress on Removal of Sr/Cs from Molten Salt in Dry Reprocessing [J]. Journal of Inorganic Materials, 2026, 41(2): 150-158.
[8]	SUN Lian, ZHANG Leilei, XUE Zexu, WU Kun, CHEN Ye, LI Zhiyuan, WANG Lukai, WANG Zungang. Research Progress on Zero-dimensional Metal Halide Scintillators towards Radiation Detection Applications [J]. Journal of Inorganic Materials, 2026, 41(2): 159-176.
[9]	REN Xianpei, LI Chao, HU Qiwei, XIANG Hui, PENG Yuehong. Research Progress on Mott-Schottky Hydrogen Evolution Catalysts Based on Metal/Transition Metal Compounds [J]. Journal of Inorganic Materials, 2026, 41(2): 137-149.
[10]	HU Yuchen, XU Zishuo, HU Yuejuan, CHEN Lidong, YAO Qin. Enhanced Thermoelectric Properties of Two-dimensional Planar Copper Polyphthalocyanine by Dispersing Single-walled Carbon Nanotubes [J]. Journal of Inorganic Materials, 2026, 41(1): 63-69.
[11]	FAN Yuzhu, WANG Yuan, WANG Linyan, XIANG Meiling, YAN Yuting, LI Benhui, LI Min, WEN Zhidong, WANG Haichao, CHEN Yongfu, QIU Huidong, ZHAO Bo, ZHOU Chengyu. Graphene Oxide-based Adsorbents for Pb(II) Removing in Water: Progresses on Synthesis, Performance and Mechanism [J]. Journal of Inorganic Materials, 2026, 41(1): 12-26.
[12]	XU Jintao, GAO Pan, HE Weiyi, JIANG Shengnan, PAN Xiuhong, TANG Meibo, CHEN Kun, LIU Xuechao. Recent Progress on Preparation of 3C-SiC Single Crystal [J]. Journal of Inorganic Materials, 2026, 41(1): 1-11.
[13]	YU Shengyang, SU Haijun, JIANG Hao, YU Minghui, YAO Jiatong, YANG Peixin. A Review of Pore Defects in Ultra-high Temperature Oxide Ceramics by Laser Additive Manufacturing: Formation and Suppression [J]. Journal of Inorganic Materials, 2025, 40(9): 944-956.
[14]	LIU Jiangping, GUAN Xin, TANG Zhenjie, ZHU Wenjie, LUO Yongming. Research Progress on Catalytic Oxidation of Nitrogen-containing Volatile Organic Compounds [J]. Journal of Inorganic Materials, 2025, 40(9): 933-943.
[15]	XIAO Xiaolin, WANG Yuxiang, GU Peiyang, ZHU Zhenrong, SUN Yong. Advances in Regulation of Damaged Skin Regeneration by Two-dimensional Inorganic Materials [J]. Journal of Inorganic Materials, 2025, 40(8): 860-870.