Cd掺杂InSb晶体生长及热电性能研究

doi:10.16553/j.cnki.issn1000-985x.2026.0022

摘要/Abstract

摘要： InSb晶体作为一种重要的III-V族窄带隙化合物半导体材料，在红外探测与成像、磁阻传感及高速电子器件等领域具有广泛应用。为进一步探索InSb晶体物理性能的多样性，本文致力于研究该晶体在热电转换领域的应用潜力。本工作采用坩埚下降法分别生长了InSb、In_0.99Cd_0.01Sb、In_0.9Cd_0.1Sb三种晶体。拉曼光谱分析表明，随着Cd掺杂浓度的增加，InSb晶体的本征峰发生了红移。Cd掺杂导致晶体导电类型由N型转变为P型，这主要归因于Cd取代In位引入了更多空穴载流子。通过Cd元素掺杂，InSb样品在最高温723 K时的热电功率因子从8.8 μW·cm^-1·K^-2提升至12.7 μW·cm^-1·K^-2。此外，由于Cd元素引入缺陷散射，样品热导率随Cd掺杂浓度升高出现显著下降，In_0.9Cd_0.1Sb晶体的室温热导率降低至8.8 W·m^-1·K^-1，在723 K时低至3.4 W·m^-1·K^-1。In_0.9Cd_0.1Sb晶体在723 K时热电优值zT取得最大值0.19。力学测试表明，Cd掺杂浓度升高会导致晶体最大压痕深度减小，硬度从2.95 GPa提高到3.15 GPa，弹性模量从56.36 GPa提高到73.54 GPa。本工作说明Cd掺杂InSb晶体在中温区具有潜在的热电应用价值。

关键词: InSb晶体; Cd掺杂; 坩埚下降法; 热电性能; 力学性能

Abstract: As an important group III-V narrow bandgap compound semiconductor，InSb crystals have been widely used in infrared detection and imaging，magnetoresistive sensing and high-speed electronic devices owing to their excellent optoelectronic and transport properties. Thermoelectric technology enables direct conversion between heat and electricity based on the Seebeck and Peltier effects. Despite their mature applications in traditional electronic fields，the potential of InSb crystals in thermoelectric energy conversion has not been fully explored. Therefore，optimizing the thermoelectric property of InSb via elemental doping is of great significance. This work systematically investigates the growth，crystal structure，thermoelectric property，and mechanical properties of Cd-doped InSb crystals. Three types of crystals，including InSb，In_0.99Cd_0.01Sb，and In_0.9Cd_0.1Sb，were grown by the Bridgman method. X-ray diffraction （XRD） analysis shows that the powder diffraction patterns agree well with the standard data，confirming a cubic zinc-blende structure with a space group of F43m. XRD pattern of the cleaved surface exhibits a single diffraction peak corresponding to the （220） plane，indicating excellent single-crystal characteristics. Scanning electron microscopy combined with energy-dispersive spectroscopy mapping confirms the homogeneous distribution of In，Sb，and doped Cd elements within the crystals. Raman spectroscopy reveals that the characteristic peaks of InSb exhibit a gradual redshift with increasing Cd doping concentration，further confirming the effective incorporation of Cd into the InSb lattice. Cd doping also induces a transition in the conduction type from N-type to P-type，which is mainly attributed to the introduction of hole carriers via Cd substitution at In sites. The pristine InSb crystal exhibits a power factor of 0.43 μW·cm^-1·K^-2 at room temperature. Upon Cd doping，the room-temperature power factor is significantly enhanced，reaching 5.9 and 5.2 μW·cm^-1·K^-2 for the In_0.99Cd_0.01Sb and In_0.9Cd_0.1Sb crystals，respectively. At 723 K，the thermoelectric power factor of the InSb sample increases from 8.8 μW·cm^-1·K^-2 to 12.7 μW·cm^-1·K^-2 by Cd doping. Meanwhile，defect scattering introduced by Cd incorporation enhances phonon scattering，leading to a significant reduction in thermal conductivity with increasing Cd concentration. The intrinsic InSb crystal exhibits a room-temperature thermal conductivity of 16.4 W·m^-1·K^-1. The thermal conductivity decreases to 8.8 W·m^-1·K^-1 for the In_0.9Cd_0.1Sb crystal at room temperature and further decreases to 3.4 W·m^-1·K^-1 at 723 K. Due to the synergistic optimization of the electrical and thermal transport properties induced by Cd doping，a thermoelectric figure of merit （zT） of 0.19 is achieved at 723 K in the In_0.9Cd_0.1Sb crystal，representing an enhancement of approximately 46% compared to that of the pristine InSb crystal. Mechanical testing indicates that an increase in Cd doping concentration leads to a reduction in the maximum indentation depth of the crystal，with the hardness increasing from 2.95 GPa to 3.15 GPa and the elastic modulus increasing from 56.36 GPa to 73.54 GPa. This work provides a feasible doping strategy for improving the thermoelectric performance of InSb crystals and demonstrates that Cd-doped InSb exhibits promising potential for thermoelectric applications in the medium-temperature range.

Key words: InSb crystal; Cd doping; Bridgman method; thermoelectric property; mechanical property

中图分类号:

师千惠, 陈浩, 林思琪, 岳晓飞, 刘学超, 金敏. Cd掺杂InSb晶体生长及热电性能研究[J]. 人工晶体学报, 2026, 55(6): 858-866.

SHI Qianhui, CHEN Hao, LIN Siqi, YUE Xiaofei, LIU Xuechao, JIN Min. Growth and Thermoelectric Properties of Cd-Doped InSb Crystals[J]. Journal of Synthetic Crystals, 2026, 55(6): 858-866.

图/表 6

图1 坩埚下降法生长InSb晶体原理图（a）及炉温曲线（b）

Fig.1 Schematic diagram of InSb crystal growth by the Bridgman method （a） and temperature profile of the furnace （b）

图2 晶体生长结果表征。InSb（a）、In0.99Cd0.01Sb（b）及In0.9Cd0.1Sb（c）晶体及其解理面；（d）多晶粉末XRD图谱；（e）（220）解理面XRD图谱；（f）In0.99Cd0.01Sb晶体SEM照片和EDS成分分布图

Fig.2 Characterization of crystal growth results. InSb （a），In0.99Cd0.01Sb （b） and In0.9Cd0.1Sb （c） crystals and the cleavage planes；（d） XRD pattern of polycrystalline powder；（e） XRD pattern of the （220） cleavage planes；（f） SEM image and EDS elemental distribution of the In0.99Cd0.01Sb crystal

图3 本征InSb、In0.99Cd0.01Sb与In0.9Cd0.1Sb晶体的拉曼光谱

Fig.3 Raman spectra of the InSb，In0.99Cd0.01Sb and In0.9Cd0.1Sb crystals

图4 电阻率（a）、塞贝克系数（b）、功率因子（c）、霍尔载流子浓度（d）及霍尔迁移率（e）、（f）与温度的依赖关系

Fig.4 Relationship of electrical resistivity （a），Seebeck coefficient （b），power factor （c），carrier concentration （d） and Hall mobility （e），（f） with temperature

图5 热导率（a）和热电优值（b）与温度的依赖关系

Fig.5 Relationship of thermal conductivity （a） and thermoelectric figure of merit （b） with temperature

图6 纳米压痕载荷-压深曲线（a）及弹性模量和硬度（b）

Fig.6 Nanoindentation load-displacement curve （a） and elastic modulus and hardness （b）

参考文献 42

[1]	MOHAN P， SENGUTTUVAN N， MOORTHY BABU S， et al. Bulk growth of InSb crystals for infrared device applications［J］. Journal of Crystal Growth， 1999， 200（1/2）： 96-100.
[2]	KORMILITSINA S S， MOLODTSOVA E V， KNYZEV S N， et al. Effect of mechanical treatment type on the strength of undoped single crystal indium antimonide wafers［J］. Modern Electronic Materials， 2020， 6（4）： 147-153.
[3]	KATS L I， SAFONOV A A， SOMOV A Y. Calculation of the magnetoresistive effect of n-InSb in strong electric fields［J］. Radiophysics and Quantum Electronics， 1977， 20（10）： 1079-1082.
[4]	KIM W Y， CHANG J， HAN S H， et al. Enhanced Hall voltage in a gate-controlled InSb Hall device［J］. Journal of Applied Physics， 2005， 97（10）： 10D507.
[5]	AVERY D G， GOODWIN D W， LAWSON W D， et al. Optical and photo-electrical properties of indium antimonide［J］. Proceedings of the Physical Society Section B， 1954， 67（10）： 761-767.
[6]	LIU P Y， MAAN J C. Optical properties of InSb between 300 and 700 K. I. Temperature dependence of the energy gap［J］. Physical Review B， 1993， 47（24）： 16274-16278.
[7]	MINOGLOU K， NELMS N， CIAPPONI A， et al. Infrared image sensor developments supported by the European Space Agency［J］. Infrared Physics & Technology， 2019， 96： 351-360.
[8]	TYO J S， GOLDSTEIN D L， CHENAULT D B， et al. Review of passive imaging polarimetry for remote sensing applications［J］. Applied Optics， 2006， 45（22）： 5453-5469.
[9]	ROGALSKI A. History of infrared detectors［J］. Opto-Electronics Review， 2012， 20（3）： 279-308.
[10]	YOSHIKAWA A， MORIYASU Y， KUZE N. High-quality InSb growth by metalorganic vapor phase epitaxy［J］. Journal of Crystal Growth， 2015， 414： 110-113.
[11]	YUAN M H， TONG Z， CAO Q， et al. Cation Mg-dominated coherent phonon transport leads to anomalous thermal conductivity in Mg₃Bi₂ ［J］. Advanced Energy Materials， 2025， 15（38）： e03481.
[12]	NAMER E， SHWARTZ S， SCHECHNER Y Y. Skyless polarimetric calibration and visibility enhancement［J］. Optics Express， 2009， 17（2）： 472.
[13]	陈继虎，路亚妮，聂　兮. 碘掺杂和多尺度结构设计提高n型碲化铅的热电性能［J］. 人工晶体学报， 2025， 54（11）： 1947-1953.
	CHEN J H， LU Y N， NIE X. Improving the thermoelectric performance of n-type lead telluride through iodine doping and multi-scale structural design［J］. Journal of Synthetic Crystals， 2025， 54（11）： 1947-1953 （in Chinese）.
[14]	高　磊，杨欣月，李文浩，等. Bi和Ag掺杂对SnTe热电性能的影响［J］. 人工晶体学报， 2024， 53（3）： 526-533.
	GAO L， YANG X Y， LI W H， et al. Effect of Bi and Ag doping on the thermoelectric property of SnTe［J］. Journal of Synthetic Crystals， 2024， 53（3）： 526-533 （in Chinese）.
[15]	PETERS M， MCNEIL L. High-pressure mössbauer study of SnSe［J］. Physical Review B， Condensed Matter， 1990， 41（9）： 5893-5897.
[16]	SNYDER G J， TOBERER E S. Complex thermoelectric materials［J］. Nature Materials， 2008， 7（2）： 105-114.
[17]	WANG Q， LI Z L， WANG J L， et al. Enhanced thermoelectric performance of InSb by regulating the carrier concentration combined with resonant level doping［J］. Small， 2026， 22（13）： e14577.
[18]	HU L P， ZHU T J， LIU X H， et al. Point defect engineering of high-performance bismuth-telluride-based thermoelectric materials［J］. Advanced Functional Materials， 2014， 24（33）： 5211-5218.
[19]	白旭东，胡皓阳，蒋　俊，等. SnSe热电半导体晶体生长技术创新进展［J］. 人工晶体学报， 2020， 49（11）： 2153-2160.
	BAI X D， HU H Y， JIANG J， et al. Progress of technological innovation of SnSe thermoelectric semiconductor crystal growth［J］. Journal of Synthetic Crystals， 2020， 49（11）： 2153-2160 （in Chinese）.
[20]	CHENG Y D， YANG J Y， JIANG Q H， et al. New insight into InSb-based thermoelectric materials： from a divorced eutectic design to a remarkably high thermoelectric performance［J］. Journal of Materials Chemistry A， 2017， 5（10）： 5163-5170.
[21]	XIN J W， JIANG Q H， WEN Y W， et al. An in situ eutectic remelting and oxide replacement reaction for superior thermoelectric performance of InSb［J］. Journal of Materials Chemistry A， 2018， 6（35）： 17049-17056.
[22]	GUO T， ZHANG G B， NAN B H， et al. Study on the effect of Sn， In， and Se co-doping on the thermoelectric properties of GeTe［J］. Materials， 2024， 17（3）： 551.
[23]	MAO J， ZHU H T， DING Z W， et al. High thermoelectric cooling performance of n-type Mg₃Bi₂-based materials［J］. Science， 2019， 365（6452）： 495-498.
[24]	VIVEKANANDAN A K， LEE C W， WU R Z， et al. Tailoring InSb nanowires for high thermoelectric performance using AAO template-assisted die casting process［J］. Nanomaterials， 2022， 12（12）： 2032.
[25]	何　峰，白旭东，陆欣昱，等. Ⅲ-Ⅵ族InSe半导体晶体生长研究进展［J］. 人工晶体学报， 2022， 51（9）： 1722-1731.
	HE F， BAI X D， LU X Y， et al. Research progress of Ⅲ-Ⅵ Group InSe semiconductor crystal growth［J］. Journal of Synthetic Crystals， 2022， 51（9）： 1722-1731 （in Chinese）.
[26]	ZHANG D， WU H， ZHOU Z Z， et al. Enhanced thermoelectric performance of InSb through deep level impurity donor state induced by La doping［J］. Materials Today Physics， 2023， 32： 101020.
[27]	NAGATA H， YAMAGUCHI S. Thermoelectric and electrical properties of Si-doped InSb thin films for a micro thermoelectric device［C］. ECS Meeting， 2008： 29.
[28]	郑　权，刘学超，王　浩，等. 铝掺杂对硒化铟晶体结构与性能的影响［J］. 人工晶体学报， 2024， 53（9）： 1528-1535.
	ZHENG Q， LIU X C， WANG H， et al. Effect of aluminum doping on the crystal structure and properties of indium selenide crystals［J］. Journal of Synthetic Crystals， 2024， 53（9）： 1528-1535 （in Chinese）.
[29]	SHI X L， LI N H， LI M， et al. Toward efficient thermoelectric materials and devices： advances， challenges， and opportunities［J］. Chemical Reviews， 2025， 125（16）： 7525-7724.
[30]	YAMAGUCHI S， MATSUMOTO T， YAMAZAKI J， et al. Thermoelectric properties and figure of merit of a Te-doped InSb bulk single crystal［J］. Applied Physics Letters， 2005， 87（20）： 201902.
[31]	ZHANG X， LU W， ZHANG Y， et al. Band convergence and thermoelectric performance enhancement of InSb via Bi doping［J］. Intermetallics， 2021， 139： 107347.
[32]	KIM D， KUROSAKI K， OHISHI Y， et al. Effect of cooling conditions on the microstructure and thermoelectric properties of Zn/Si-codoped InSb［J］. Journal of Electronic Materials， 2013， 42（7）： 2388-2392.
[33]	ABAKER M， AHMED N E， SAAD A， et al. Thermoelectric properties of Ga-doped InSb alloys［J］. Vacuum， 2024， 219： 112761.
[34]	YU P Y， SHEN Y R. Effect of doping on the resonance Raman scattering in InSb near the E1 transition［M］//Proceedings of the Twelfth International Conference on the Physics of Semiconductors. Wiesbaden： Vieweg+Teubner Verlag， 1974： 453-457.
[35]	LOURDHUSAMY V， CHEN J L， PAULRAJ I， et al. Enhanced thermoelectric performance of polycrystalline InSb_1- _x Bi _x by using isoelectronic substitution on the Sb site［J］. Journal of Alloys and Compounds， 2022， 920： 165949.
[36]	CIESIELSKI K， KACZOROWSKI D. On electrical transport and thermoelectric performance in Half-Heusler phase ScNiSb［J］. International Journal of Modern Physics B， 2024， 38（6）： 2450084.
[37]	SHI X L， LIU W D， LI M， et al. A solvothermal synthetic environmental design for high-performance SnSe-based thermoelectric materials［J］. Advanced Energy Materials， 2022， 12（20）： 2200670.
[38]	EHRENREICH H. Transport of electrons in intrinsic InSb［J］. Journal of Physics and Chemistry of Solids， 1959， 9（2）： 129-148.
[39]	ZHANG Q H， HUANG X Y， BAI S Q， et al. Thermoelectric devices for power generation： recent progress and future challenges［J］. Advanced Engineering Materials， 2016， 18（2）： 194-213.
[40]	ROYCHOWDHURY S， GHOSH T， ARORA R， et al. Enhanced atomic ordering leads to high thermoelectric performance in AgSbTe₂ ［J］. Science， 2021， 371（6530）： 722-727.
[41]	ZHANG H L， JIN M， SHEN H， et al. Influence of Si doping on dislocations and mechanical properties of GaAs crystals grown by modified vertical bridgman method［J］. Crystal Research and Technology， 2022， 57（7）： 2100247.
[42]	LE BOURHIS E， PATRIARCHE G. Nanoindentation investigation of solid-solution strengthening in III-V semiconductor alloys［J］. International Journal of Materials Research， 2022， 96（11）： 1237-1241.