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]

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

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