区熔法制备金属硫化物Ag2S及其热电性能研究

doi:10.15541/jim20200653

摘要/Abstract

摘要：

金属硫化物Ag₂S具有优异的物理化学性能, 在催化、传感及光电子等领域具有广阔的应用空间。本工作利用一种区熔技术制备了尺寸为ϕ18 mm×50 mm的Ag₂S并对其潜在热电性能进行了研究。Ag₂S在450 K以下具有标准的α-Ag₂S单斜P2₁/c结构, 450 K以上发生相变成为立方β-Ag₂S相。Ag₂S在300~650 K范围始终具有负的Seebeck系数而呈现n型半导体特征, 这主要是因为材料中存在Ag间隙离子而提供了多余电子。Ag₂S的Seebeck系数在室温下约为-1200 µV·K^-1, 440 K时降为-680 µV·K ^-1, 当转变为β-Ag₂S后则大幅降至~-100 µV·K^-1。α-Ag₂S的电导率几乎为零, 然而在刚发生β-Ag₂S相变(450 K)时, 电导率突然增加至~40000.5 S·m^-1, 而后随着温度持续升高, 其值在650 K降低为33256.2 S·m^-1。霍尔测试表明Ag₂S的载流子浓度n_H在相变时可从~10¹⁷ cm^-3迅速增加到~10¹⁸ cm^-3量级。α-Ag₂S和β-Ag₂S的总热导率κ几乎是常数, 分别为~0.20和~0.45 W·m^-1·K^-1。最终Ag₂S在580 K获得最大ZT值0.57, 说明它是一种很有发展潜力的中温热电材料。

关键词: Ag₂S, 区熔, 热电材料, 相转变

Abstract:

Metal sulfide Ag₂S is an attractive semiconductor due to its excellent physical and chemical property that enable it with wide applications in fields of catalysis, sensing, optoelectronics in past years. In present work, ϕ18 mm× 50 mm Ag₂S ingot was successfully prepared using zone melting method and its thermoelectric (TE) behavior was investigated. Ag₂S has standard monoclinic P2₁/c space group (α-Ag₂S phase) below 450 K and transfer to cubic structure (β-Ag₂S phase) over this temperature. Ag₂S is a n-type semiconductor as the Seebeck coefficient S is always negative due to the Ag interstitial ions in the material that can provide additional electrons. S is about -1200 µV·K^-1near room temperature, declines to -680 µV·K ^-1 at 440 K and finally decreases to ~-100 µV·K ^-1at β-Ag₂S state. The electrical conductivity (σ) of α-Ag₂S is almost zero. However, the value sharply jumps to ~40000.5 S·m ^-1 as the material just changes to β-Ag₂S at 450 K and then gradually deceases to 33256.2 S·m ^-1 at 650 K. Hall measurement demonstrates that carrier concentration n_H of Ag₂S is suddenly increased from the level of ~10 ¹⁷ cm^-3 to ~10¹⁸ cm^-3during phase transition. Total thermal conductivity κ of α-Ag₂S is ~0.20 W·m ^-1·K^-1 but is ~0.45 W·m^-1·K^-1of β-Ag₂S. Ultimately, a maximum ZT=0.57 is achieved around 580 K that means Ag₂S might be a promising middle-temperature TE material.

Key words: Ag₂S, zone melting, thermoelectric material, phase transition

中图分类号:

TQ174

金敏, 白旭东, 张如林, 周丽娜, 李荣斌. 区熔法制备金属硫化物Ag₂S及其热电性能研究[J]. 无机材料学报, 2022, 37(1): 101-106.

JIN Min, BAI Xudong, ZHANG Rulin, ZHOU Lina, LI Rongbin. Metal Sulfide Ag₂S: Fabrication via Zone Melting Method and Its Thermoelectric Property[J]. Journal of Inorganic Materials, 2022, 37(1): 101-106.

图/表 9

Table 1 Parameters for Ag2S fabrication

Parameter	Zone melting
Weight of raw material/g	60.5
Quartz ampoule size/mm	ϕ18
Vacuum of quartz ampoule/Pa	<10^-2
Furnace temperature/℃	920
Temperature gradient/(℃·cm^-1)	30-35
Lowering speed/(mm·h^-1)	3.0

Fig. 1 Schematic diagram of the zone melting furnace (a) and temperature profile along vertical direction (b)

Fig. 2 Ag2S ingot prepared by zone melting method

Fig. 3 XRD pattern (a) and EDS map (b) of Ag2S

Fig. 4 SEM images of original Ag2S surface (a), Ag particles on Ag2S matrix (b) and enlarged morphology of the surface (c)

Fig. 5 Relationship of Seebeck (a), electrical conductivity σ (b) and power factor PF (c) with temperature

Fig. 6 Carrier concentration nH (a) and mobility µH (b) vs temperature

Fig. 7 Relationship between κ and temperature

Fig. 8 Dependence of ZT with temperature

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区熔法制备金属硫化物Ag₂S及其热电性能研究

Metal Sulfide Ag₂S: Fabrication via Zone Melting Method and Its Thermoelectric Property

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