Nonequilibrium Layered PbS Stabilized by Sn Doping: Bipolar Semiconductors with Low Thermal Conductivity

IF 4.3 3区 材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC ACS Applied Electronic Materials Pub Date : 2024-11-08 DOI:10.1021/acsaelm.4c0157210.1021/acsaelm.4c01572
Mari Hiramatsu, Zhongxu Hu, Sakura Yoshikawa, Zan Yang, Xinyi He, Takayoshi Katase*, Jun-ichi Yamaura, Hajime Sagayama, Terumasa Tadano, Shigenori Ueda, Hidenori Hiramatsu, Hideo Hosono and Toshio Kamiya*, 
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Abstract

Layered Sn- and Ge-based monochalcogenides have been known as promising semiconductor materials with appropriately narrow band gaps close to those of Si and GaAs. On the other hand, Pb-based ones possess much narrower band gaps and adopt the cubic rock-salt (RS)-type structure under ambient conditions, and their layered structures are considered thermodynamically unstable. We recently succeeded in the stabilization of GeS-type layered structures in lightly Sn-doped PbS by the combination of a high-temperature solid-state reaction with thermal quenching. In this paper, we have comprehensively investigated the relationship between the crystal structures, electronic structures, and also electronic and thermal transport properties of (Pb1–xSnx)S (x = 0–1). It is experimentally confirmed that an equilibrium phase of layered GeS-type Sn-rich (Pb1–xSnx)S is a p-type semiconductor at x ≥ 0.7, whereas n-type conduction is observed at x = 0.5 and 0.6. In contrast, the stabilized nonequilibrium layered phase with 0.2 ≤ x ≤ 0.4 is an n-type semiconductor with the band gaps of 1.18–1.22 eV, and the electron density increases up to 6.4 × 1017 cm–3 in (Pb0.8Sn0.2)S. Furthermore, the layered nonequilibrium phase exhibits an ultralow room-temperature thermal conductivity of 0.40–0.65 W/(mK), much lower than those of both end members, i.e., GeS-type SnS (x = 1) and RS-type PbS (x = 0). Based on first-principles electron and phonon transport calculations, layered n-type (Pb0.75Sn0.25)S potentially shows a high thermoelectric figure of-merit of 0.34 even at 300 K under an optimized electron concentration. The controllability of bipolar carrier polarity in layered (Pb1–xSnx)S alongside the low thermal conductivity is an advantageous characteristic for applications based on p–n homojunctions, such as photovoltaics and thermoelectrics.

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通过掺杂锡稳定的非平衡层状 PbS:具有低导热性的双极半导体
层状锡基和锗基单粲化合物具有接近硅和砷化镓的适当窄带隙,是一种很有前途的半导体材料。另一方面,铅基单质具有更窄的带隙,在环境条件下呈立方体岩盐(RS)型结构,其层状结构被认为在热力学上是不稳定的。最近,我们通过高温固态反应与热淬火相结合的方法,成功地稳定了轻度掺锡 PbS 中的 GeS 型层状结构。本文全面研究了 (Pb1-xSnx)S (x = 0-1) 的晶体结构、电子结构以及电子和热传输特性之间的关系。实验证实,层状 GeS 型富锡 (Pb1-xSnx)S 的平衡相在 x ≥ 0.7 时是 p 型半导体,而在 x = 0.5 和 0.6 时则是 n 型传导。相反,0.2 ≤ x ≤ 0.4 的稳定非平衡层状相是一种 n 型半导体,带隙为 1.18-1.22 eV,电子密度在(Pb0.8Sn0.2)S 中增加到 6.4 × 1017 cm-3。此外,层状非平衡相的室温热导率为 0.40-0.65 W/(mK),远低于两个端成员(即 GeS 型 SnS(x = 1)和 RS 型 PbS(x = 0))的室温热导率。根据第一原理电子和声子输运计算,层状 n 型(Pb0.75Sn0.25)S 在优化的电子浓度下,即使在 300 K 时也可能显示出 0.34 的高热电功率。层状(Pb1-xSnx)S 中双极载流子极性的可控性以及低热导率是基于 p-n 同结的应用(如光伏和热电)的有利特性。
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来源期刊
CiteScore
7.20
自引率
4.30%
发文量
567
期刊介绍: ACS Applied Electronic Materials is an interdisciplinary journal publishing original research covering all aspects of electronic materials. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials science, engineering, optics, physics, and chemistry into important applications of electronic materials. Sample research topics that span the journal's scope are inorganic, organic, ionic and polymeric materials with properties that include conducting, semiconducting, superconducting, insulating, dielectric, magnetic, optoelectronic, piezoelectric, ferroelectric and thermoelectric. Indexed/​Abstracted: Web of Science SCIE Scopus CAS INSPEC Portico
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