Article(id=1256186033012618228, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, articleNumber=null, orderNo=null, doi=10.11858/gywlxb.20261005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1767801600000, receivedDateStr=2026-01-08, revisedDate=1770480000000, revisedDateStr=2026-02-08, acceptedDate=null, acceptedDateStr=null, onlineDate=1777427689078, onlineDateStr=2026-04-29, pubDate=1775318400000, pubDateStr=2026-04-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1777427689078, onlineIssueDateStr=2026-04-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1777427689078, creator=13701087609, updateTime=1777427689078, updator=13701087609, issue=Issue{id=1256186027853624275, tenantId=1146029695717560320, journalId=1255847867265597444, year='2026', volume='40', issue='4', pageStart='040101-1', pageEnd='045301-13', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1777427687845, creator=13701087609, updateTime=1777427791253, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1256186461888627074, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1256186461888627075, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1256186027853624275, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=040101-1, endPage=040101-10, ext={EN=ArticleExt(id=1256186034270909438, articleId=1256186033012618228, tenantId=1146029695717560320, journalId=1255847867265597444, language=EN, title=Crystal Structure and Transport Properties of LaZn1–δSb2 under Pressure, columnId=1256186029531345878, journalTitle=Chinese Journal of High Pressure Physics, columnName=Young Scientists’ Forum, runingTitle=null, highlight=null, articleAbstract=

In the search of new superconducting materials, some specific structural units are recognized as essential factors for the emergence of superconductivity, such as the CuO2 planes in cuprates and the Fe-As layers in iron-based superconductors. In this study, we investigate the structural and transport properties of the zinc-based 112-type compound LaZn1–δSb2 with Zn-Sb layers at both ambient and high pressures. The LaZn1–δSb2 crystallizes in a tetragonal structure with a certain amount of Zn vacancies at ambient pressure. The low-temperature physical properties exhibit paramagnetic metallic behavior, with resistivity showing anisotropy behavior, and the magnetoresistance is positive at low temperatures. Meanwhile, the hole-type Hall coefficient shows significant temperature dependence, indicating that the transport behavior is dominated by multiband effects. Under high pressures, LaZn1–δSb2 retains its tetragonal phase while undergoing a volume compression exceeding 25%. As pressure increases, the absolute value of resistance and residual resistance ratio initially decrease and then increase. Further fitting reveals that the transport behavior under pressure remains dominated by electron-phonon scattering and shows almost no pressure dependence. Notably, no superconductivity above 2 K is observed up to the highest pressure of 50.9 GPa in this study. The absence of superconductivity in LaZn1–δSb2 may be related to lattice defects induced by Zn vacancies. These results can provide useful insights for the search for new superconductivity in compounds with similar structures.

, correspAuthors=Qing LI, Haihu WEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Chinese Journal of High Pressure Physics. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Zhening XIANG, Qing LI, Haihu WEN), CN=ArticleExt(id=1256186050163126447, articleId=1256186033012618228, tenantId=1146029695717560320, journalId=1255847867265597444, language=CN, title=高压下LaZn1–δSb2的结构及输运性质, columnId=1256186029946581977, journalTitle=高压物理学报, columnName=优秀青年专辑, runingTitle=null, highlight=null, articleAbstract=

在新超导材料的探索中,某些特定的结构单元被认为对超导的产生至关重要,如铜氧和铁基高温超导体中的CuO2面和Fe-As层等。为此,研究了具有Zn-Sb层的锌基112型LaZn1–δSb2在常压和高压下的结构和输运性质。研究发现:LaZn1–δSb2在常压下具有四方结构,并存在一定的Zn空位;其低温物理性质表现出顺磁金属行为,具有一定的各向异性和正磁阻现象;同时,空穴型霍尔系数随温度变化明显,表明该材料的输运行为由多带效应主导。在高压下,LaZn1–δSb2依然维持四方结构,但是体积被压缩超过25%;与此同时,高压下的绝对电阻值以及剩余电阻比均随压力的升高先减小后增大。进一步拟合发现,压力下LaZn1–δSb2的输运行为依然由电子-声子散射主导,且几乎不随压力变化。在所测试的最高达50.9 GPa的压力下,没有观测到2 K以上的超导现象;LaZn1–δSb2中超导电性的缺失可能与Zn空位导致的晶格缺陷有关。该研究结果可为探索同类结构化合物中的新型超导电性提供有意义的参考。

, correspAuthors=李庆, 闻海虎, authorNote=null, correspAuthorsNote=
李 庆(1991-),男,博士,助理教授,主要从事新型超导材料探索和压力下的性质调控研究. E-mail:
闻海虎(1964-),男,博士,教授,主要从事新型超导材料的探索合成、高温超导材料的超导机理和超导体磁通动力学研究. E-mail:
, copyrightStatement=版权所有©《高压物理学报》编辑部 2026, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=6xiXmmozZZgJv4llsz77iQ==, magXml=0Vw1iDJKzR9PWNpTJwVm4Q==, pdfUrl=null, pdf=g9PsSprwxMszR1aK74BthA==, pdfFileSize=3240691, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=SoY3jzPXmgTkBygo3yCEfQ==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=pjDr73I99tGAkKY8WOnCdQ==, mapNumber=null, authorCompany=null, fund=null, authors=

项浙宁(2001-),男,博士研究生,主要从事高压下超导材料的输运测量和物理性质研究. E-mail:

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项浙宁(2001-),男,博士研究生,主要从事高压下超导材料的输运测量和物理性质研究. E-mail:

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figs=[ArticleFig(id=1256186057360552213, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.1, caption=Schematic diagram of the crystal structure of LaZn1–δSb2, figureFileSmall=x0DDSxKbOIr5VpV3BKZplg==, figureFileBig=SoY3jzPXmgTkBygo3yCEfQ==, tableContent=null), ArticleFig(id=1256186057624793367, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图1, caption=LaZn1–δSb2的晶体结构示意图, figureFileSmall=x0DDSxKbOIr5VpV3BKZplg==, figureFileBig=SoY3jzPXmgTkBygo3yCEfQ==, tableContent=null), ArticleFig(id=1256186058191024413, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.2, caption=Photo of LaZn1–δSb2 single crystals, figureFileSmall=Vnh7tnB2xcfaOup4BdaL7g==, figureFileBig=QhOZeTbLU1eyxEiiDGiK5Q==, tableContent=null), ArticleFig(id=1256186058543345950, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图2, caption=LaZn1–δSb2单晶照片, figureFileSmall=Vnh7tnB2xcfaOup4BdaL7g==, figureFileBig=QhOZeTbLU1eyxEiiDGiK5Q==, tableContent=null), ArticleFig(id=1256186058971164959, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.3, caption=(a) Typical EDS of LaZn1–δSb2 (Inset shows the atomic concentration of different elements.); (b) XRD pattern of the single crystal, showing that the largest natural face is ab-plane; (c) temperature dependence of magnetic susceptibility (χ-T) curve measured with an external field of 1 T (The solid red line is the Curie-Weiss fitting line.), figureFileSmall=NppDJDLq4WZP6oo92Ihgdw==, figureFileBig=/r6ArHMcaXzJF2eX7KBJSA==, tableContent=null), ArticleFig(id=1256186059407372577, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图3, caption=(a) LaZn1–δSb2的典型EDS(插图表格为各元素的原子分数);(b) 单晶样品的 XRD谱(最大自然解离晶面为 ab 面);(c) 外加磁场为 1 T时测得的χ-T曲线(红色实线为居里-外斯拟合曲线), figureFileSmall=NppDJDLq4WZP6oo92Ihgdw==, figureFileBig=/r6ArHMcaXzJF2eX7KBJSA==, tableContent=null), ArticleFig(id=1256186059717751078, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.4, caption=(a) Temperature dependence of normalized resistance (ρ/ρ300 K-T) of LaZn1–δSb2 from 2 K to 300 K with current along different directions; (b) magnetic field-dependent magnetoresistance (MR) at different temperatures, and a large positive magnetoresistance effect (38%) is observed at 9 T and 2 K; (c) the Hall resistivity versus magnetic field at selected temperatures; (d) temperature dependence of Hall coefficient (RH-T) at ambient pressure, figureFileSmall=xJPpy6rj5lJqoDxsQPRbbQ==, figureFileBig=Q5k+cAHlA6QG+cyfYh32Iw==, tableContent=null), ArticleFig(id=1256186060170735913, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图4, caption=(a) 电流沿不同方向时LaZn1–δSb2在2~300 K温度范围内的归一化电阻率-温度依赖关系(ρ/ρ300 K-T),(b) 不同温度下磁阻的磁场依赖关系曲线(在 9 T 磁场和 2 K 温度下观察到较大(38%)的正磁电阻效应),(c) 不同温度下的霍尔电阻率与磁场的关系曲线,(d) 常压下霍尔系数的温度依赖关系(RH-T, figureFileSmall=xJPpy6rj5lJqoDxsQPRbbQ==, figureFileBig=Q5k+cAHlA6QG+cyfYh32Iw==, tableContent=null), ArticleFig(id=1256186060611137840, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.5, caption=(a) XRD patterns of LaZn1–δSb2 collected at different pressures up to 52.6 GPa; (b) pressure dependence of lattice constants; (c) the derived cell volume as a function of pressure for LaZn1–δSb2 (The solid red line is the third-order B-M fitting curve.), figureFileSmall=uF5rbwHJo2Tqk64hadjAdw==, figureFileBig=eoQRA4UfVzID2Dw7gDAq1w==, tableContent=null), ArticleFig(id=1256186060778910002, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图5, caption=(a) 最高至52.6 GPa时不同压力下LaZn1–δSb2的同步辐射XRD谱,(b) 晶格常数的压力依赖关系,(c) 计算得到的LaZn1–δSb2晶胞体积与压力的关系曲线(红色实线为三阶 B-M 拟合曲线), figureFileSmall=uF5rbwHJo2Tqk64hadjAdw==, figureFileBig=eoQRA4UfVzID2Dw7gDAq1w==, tableContent=null), ArticleFig(id=1256186061143814452, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.6, caption=Rietveld refinement XRD patterns of LaZn1–δSb2 at (a) 2.7 GPa and (b) 52.6 GPa (All the curves can be fitted using the same space group (P4/nmm) as that of the ambient pressure structure.), figureFileSmall=HJmCZlT9UfHelmzOc0m6Fg==, figureFileBig=J8eyzXp9Fcd8BtvEx4XqGw==, tableContent=null), ArticleFig(id=1256186061479358774, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图6, caption=LaZn1–δSb2在(a) 2.7 GPa和(b) 52.6 GPa下的XRD谱Rietveld 精修结果(所有曲线都可以用与常压结构相同的四方结构(空间群 P4/nmm)进行拟合), figureFileSmall=HJmCZlT9UfHelmzOc0m6Fg==, figureFileBig=J8eyzXp9Fcd8BtvEx4XqGw==, tableContent=null), ArticleFig(id=1256186061852651833, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=EN, label=Fig.7, caption=(a)–(b) Temperature dependence of resistance (R-T) curves for LaZn1–δSb2 under various pressures up to 50.9 GPa; (c) normalized R-T curves of LaZn1–δSb2 at selected pressures (Inset shows the pressure dependent R300 K/R2 K of LaZn1–δSb2.); (d) the evolution of the n value with pressure (The formula $ R\left(T\right)={R }_{0}+A{T}^{n} $ was used to fitting the R-T curves at various pressures in the temperature region from 2 to 50 K.), figureFileSmall=5mJ7CNhOjL8j/MZenAOftA==, figureFileBig=SA/nK+E0jkU6IGzuPkEKqA==, tableContent=null), ArticleFig(id=1256186062674735419, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1256186033012618228, language=CN, label=图7, caption=(a)~(b) 最高至50.9 GPa时不同压力下LaZn1–δSb2的电阻-温度(R-T)依赖关系曲线,(c) 不同压力下 LaZn1–δSb2的归一化电阻-温度(R/R300 K-T)曲线(插图为 LaZn1–δSb2R300 K/R2 K随压力的变化曲线),(d) 温度项的幂指数n随压力的演变规律(采用$ R \left(T\right)={R }_{0}+A{T}^{n} $对 2~50 K 温度区间内不同压力下的R-T 曲线进行拟合的结果), figureFileSmall=5mJ7CNhOjL8j/MZenAOftA==, figureFileBig=SA/nK+E0jkU6IGzuPkEKqA==, tableContent=null)], attaches=null, journal=Journal(id=1255846718311514113, delFlag=0, nameCn=高压物理学报, nameEn=Chinese Journal of High Pressure Physics, nameHistory1=null, nameHistory2=null, issn=1000-5773, eissn=null, cn=51-1147/O4, coden=null, periodic=0, language=CN, oaType=null, ccby=null, superviseOffice=null, ownerOffice=null, pubOffice=null, editorOffice=null, officeType=null, aims=null, clcCode=null, officeProv=null, officeCity=null, officeAddr=null, officeZip=null, officeEmail=null, officePhone=null, editDirector=null, officeDirector=null, officeDirectorPhone=null, officeStaffNum=null, officeEmpNum=null, coverPicUrl=KWePOcsfwWv2cMGG6VIsRw==, journalPrice=null, startedYear=null, 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高压下LaZn1–δSb2的结构及输运性质
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项浙宁 , 李庆 * , 闻海虎 *
高压物理学报 | 优秀青年专辑 2026,40(4): 040101-1-040101-10
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高压物理学报 | 优秀青年专辑 2026, 40(4): 040101-1-040101-10
高压下LaZn1–δSb2的结构及输运性质
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项浙宁 , 李庆* , 闻海虎*
作者信息
  • 南京大学物理学院超导物理与材料研究中心, 江苏 南京 210093
  • 项浙宁(2001-),男,博士研究生,主要从事高压下超导材料的输运测量和物理性质研究. E-mail:

通讯作者:

李 庆(1991-),男,博士,助理教授,主要从事新型超导材料探索和压力下的性质调控研究. E-mail:
闻海虎(1964-),男,博士,教授,主要从事新型超导材料的探索合成、高温超导材料的超导机理和超导体磁通动力学研究. E-mail:
Crystal Structure and Transport Properties of LaZn1–δSb2 under Pressure
Zhening XIANG , Qing LI* , Haihu WEN*
Affiliations
  • Center for Superconducting Physics and Materials, Department of Physics, Nanjing University, Nanjing 210093, Jiangsu, China
出版时间: 2026-04-05 doi: 10.11858/gywlxb.20261005
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在新超导材料的探索中,某些特定的结构单元被认为对超导的产生至关重要,如铜氧和铁基高温超导体中的CuO2面和Fe-As层等。为此,研究了具有Zn-Sb层的锌基112型LaZn1–δSb2在常压和高压下的结构和输运性质。研究发现:LaZn1–δSb2在常压下具有四方结构,并存在一定的Zn空位;其低温物理性质表现出顺磁金属行为,具有一定的各向异性和正磁阻现象;同时,空穴型霍尔系数随温度变化明显,表明该材料的输运行为由多带效应主导。在高压下,LaZn1–δSb2依然维持四方结构,但是体积被压缩超过25%;与此同时,高压下的绝对电阻值以及剩余电阻比均随压力的升高先减小后增大。进一步拟合发现,压力下LaZn1–δSb2的输运行为依然由电子-声子散射主导,且几乎不随压力变化。在所测试的最高达50.9 GPa的压力下,没有观测到2 K以上的超导现象;LaZn1–δSb2中超导电性的缺失可能与Zn空位导致的晶格缺陷有关。该研究结果可为探索同类结构化合物中的新型超导电性提供有意义的参考。

高压  /  超导电性  /  LaZn1–δSb2  /  高压同步辐射  /  费米液体行为

In the search of new superconducting materials, some specific structural units are recognized as essential factors for the emergence of superconductivity, such as the CuO2 planes in cuprates and the Fe-As layers in iron-based superconductors. In this study, we investigate the structural and transport properties of the zinc-based 112-type compound LaZn1–δSb2 with Zn-Sb layers at both ambient and high pressures. The LaZn1–δSb2 crystallizes in a tetragonal structure with a certain amount of Zn vacancies at ambient pressure. The low-temperature physical properties exhibit paramagnetic metallic behavior, with resistivity showing anisotropy behavior, and the magnetoresistance is positive at low temperatures. Meanwhile, the hole-type Hall coefficient shows significant temperature dependence, indicating that the transport behavior is dominated by multiband effects. Under high pressures, LaZn1–δSb2 retains its tetragonal phase while undergoing a volume compression exceeding 25%. As pressure increases, the absolute value of resistance and residual resistance ratio initially decrease and then increase. Further fitting reveals that the transport behavior under pressure remains dominated by electron-phonon scattering and shows almost no pressure dependence. Notably, no superconductivity above 2 K is observed up to the highest pressure of 50.9 GPa in this study. The absence of superconductivity in LaZn1–δSb2 may be related to lattice defects induced by Zn vacancies. These results can provide useful insights for the search for new superconductivity in compounds with similar structures.

high-pressure  /  superconductivity  /  LaZn1–δSb2  /  high-pressure synchrotron diffraction  /  Fermi-liquid behavior
项浙宁, 李庆, 闻海虎. 高压下LaZn1–δSb2的结构及输运性质. 高压物理学报, 2026 , 40 (4) : 040101-1 -040101-10 . DOI: 10.11858/gywlxb.20261005
Zhening XIANG, Qing LI, Haihu WEN. Crystal Structure and Transport Properties of LaZn1–δSb2 under Pressure[J]. Chinese Journal of High Pressure Physics, 2026 , 40 (4) : 040101-1 -040101-10 . DOI: 10.11858/gywlxb.20261005
2008年,日本科学家Hosono在铁基La[O1–xFx]FeAs体系中发现了26 K的超导电性,这一发现激发了人们在铁基材料中探索高温超导体的兴趣[1]。随后,在2013年,Sawa课题组[2]首次成功合成了112型铁基超导体Ca1–xLaxFeAs2。晶体结构解析表明,该化合物属于单斜晶系,空间群为 P21,明显区别于传统铁基超导体中常见的四方或正交对称结构。电输运和磁化测量结果表明,在名义掺杂x=0.10的样品中,超导转变温度(Tc)达到39 K,零电阻转变温度为36 K,超导体积分数约为66%。除了La掺杂之外,Yakita等[3]也对相同结构的Ca1–xPrxFeAs2体系进行了系统的研究,在约20 K观测到超导转变,进一步证实了112型铁基材料中超导电性的普适性。2016年,中国科学院物理研究所Yu等[4]成功合成了新型112型铁基材料EuFeAs2,通过La元素对Eu位进行化学掺杂,在Eu1–xLaxFeAs2体系中成功诱导出超导电性。随着La掺杂浓度的提高,材料中原本存在的2个反铁磁相均受到明显抑制,同时超导转变温度逐渐上升,在x=0.15时达到最高Tc (约11 K)。与先前难以获得母体化合物的Ca1–xLaxFeAs2体系不同,EuFeAs2为研究通过电子掺杂从反铁磁母体演化至超导态提供了理想的材料研究平台。进一步地,研究人员在Fe位掺杂Ni、Pd和Co等元素的研究中均观察到了超导现象[59],其中EuFe0.9Co0.1As2表现出最高的Tc,达到28 K[10]。值得注意的是,112型结构也存在于铜基和镍基超导体中,如CaCuO2和LaNiO2[1113],但该类112型结构与铁基体系的关键差异在于:具有锯齿形As链的FeAs层在这些材料中被平整的CuO2面或NiO2面所替代。上述准二维结构单元也被认为是产生高温超导的关键结构基础。因此,在其他112型结构体系中进一步探索新型超导材料,对于揭示高温超导电性的普适物理机制、理解不同结构单元对超导态的影响具有重要的科学意义。
鉴于对铁基112型结构及其超导性能的广泛关注,相关研究也被拓展至具有相似层状特征的其他过渡金属基112型化合物体系,以期在其中发现与铁基超导体类似的非常规超导电性。经过前期的系统调研,本课题组发现,层状112型锑化物ReTSb2(Re=La~Nd, Sm, Gd, Tb; T 为过渡金属)作为一类典型的具有准二维T-Sb结构的层状金属间化合物[1420],具有丰富的物理性质,因而备受关注。该类化合物均为四方ZrCuSi2型结构,其核心结构单元是T-Sb层组成的准二维结构单元,与铁基超导体的Fe-As层类似。有趣的是,该类化合物中的部分材料在低温下表现出电荷密度波(charge density wave,CDW)序与超导序的相互竞争关系。例如:在常压下,LaAgSb2具有较高的CDW转变温度(TCDW1≈207 K, TCDW2≈186 K)[1415],低温下存在Tc≈0.3 K的超导电性[19];LaAuSb2在低温下同样存在CDW转变(TCDW≈88 K)与超导(Tc≈0.64 K)的共存[1618]。虽然高温下LaCuSb2、LaNiSb2和LaPdSb2不存在CDW转变,但是低温下分别存在0.9、1.0和2.7 K的超导电性[17]。到目前为止,在112型ReTSb2系列化合物中,只有上述几种材料表现出超导电性,并且超导转变温度都比较低,更无法与铁基等高温超导体中的112型结构化合物相比拟。因此,在该类材料中探索新的可能的超导电性,为深入理解特定结构对超导电性的支撑作用以及CDW与SC的竞争和共存关系提供了很好的研究课题。压力作为一种有效且干净的物性调控手段,可以在不引入化学杂质的前提下连续、清洁地调控材料的物理性质。对于具有准二维特性的材料,压力可以明显地增强沿c轴方向的层间耦合,促使材料的电子结构从二维向三维过渡。例如,在LaAgSb2中,这种“三维化”效应直接破坏了Sb方网层中费米面的理想嵌套条件,从而导致CDW序被系统性抑制[20]。当达到CDW被完全抑制的临界压力(约3.2 GPa)时,Tc出现显著增强,从常压下的0.3 K急剧提升至近1 K,增幅超过3倍[19]
锌(Zn)元素作为与铜相邻的3d过渡金属族元素,Zn基112型化合物 LaZn1–δSb2具有同样的四方结构对称性,空间群为P4/nmm。LaZn1–δSb2的结构由Zn-Sb层和四方的Sb网状层交替堆叠构成,La原子则填充在层间的空隙中,形成独特的二维层状结构[2122],如图1所示。以往研究发现,该化合物中存在一定的本征Zn空位,其实际化学组分更接近于LaZn0.6Sb2,且没有明显的成分变化区间。过渡金属T位缺陷被认为是该类结构的一种本征特性,与电子结构的稳定性有关[23]。研究表明,LaZn0.6Sb2在常压下表现出典型的金属性行为,其面内电阻率随温度的降低而单调下降。磁化率测量发现,LaZn0.6Sb2在温度低至2 K时仍未出现任何长程磁有序。除了低温区的微弱上翘外,其磁化率在所测温度范围内基本保持恒定,表现出典型的泡利顺磁行为[23]。然而,目前对该材料系统的物理性质研究,尤其是在高压下的结构和输运行为研究还比较缺乏。研究压力对其晶体结构和电输运行为的调控,探索压力诱导可能的结构相变和超导电性,将是一个非常有意义的研究课题。
本研究将通过原位高压同步辐射X射线衍射(X-ray diffraction,XRD)和高压输运实验探索高压下LaZn1–δSb2的结构和输运性质的演变规律,旨在通过高压这一纯净的物性调控手段,探究该体系在压力作用下的结构和输运行为演化以及可能的超导电性。相关研究结果将有助于加深对112型结构及其物理性质的认识,为后续在该类材料中使用元素替代或掺杂方式获得超导电性等研究提供有益的参考。
采用助熔剂法[16]制备LaZn1–δSb2单晶样品。首先,将高纯度(99.9%)的La块、Zn粉和Sb粉按1∶2∶20的摩尔比称量,充分混合后,置于氧化铝坩埚中。然后,在充满惰性气氛的环境中将坩埚密封于石英管内。初始反应原料中过量的Sb用作样品生长过程中的助熔剂,而过量的Zn则为了减少目标产物中Zn位缺陷的产生。接着,将封装好的样品置于马弗炉中进行生长,具体的生长流程为:在10 h内将样品加热至1050 ℃,保温8 h,随后以2 ℃/h的速率缓慢冷却至750 ℃,以促使单晶生长。最后,通过高速离心分离与机械剥离移除过量的Sb助熔剂,获得片状LaZn1–δSb2单晶。单晶样品实物如图2所示,尺寸为1~2 mm。
通过粉末X射线衍射仪(Bruker D8 Advanced)和扫描电子显微镜(PhenomProX)完成常压下的结构和成分表征。材料的晶体结构通过VESTA软件[24]进行绘制。低温下的电阻和磁化率测试分别在Quantum Design公司生产的综合物性测量仪(PPMS-9T)和磁性测量系统(MPMS3)上完成。在常压面内电阻率和霍尔电阻率测试中,使用标准5引线法。对于电流沿c轴方向的电阻率,则使用Corbino型电极排布[25]
高压实验在金刚石对顶砧(diamond anvil cell,DAC)中进行。为了达到约50 GPa的压力,采用直径为300 µm的金刚石压砧对样品施加压力。垫片材料为T301不锈钢。首先,在垫片中心利用金刚石压砧预压出凹痕,再通过激光打孔技术制备直径为200 µm的微孔作为样品腔。为隔绝样品与金属垫片之间的电接触,使用立方氮化硼(c-BN)作为绝缘层。然后,将待测样品、红宝石以及KBr传压介质填充至样品腔内。样品的原位压力通过红宝石在压力下的荧光特征峰位移标定[26]。样品通过4根铂电极和外部导线与综合物性测量仪连接,采用范德堡构型的四电极排布方式进行高压输运测量。
高压同步辐射XRD测试在上海同步辐射光源(Shanghai Synchrotron Radiation Facility,SSRF)的BL15U1线站上进行,入射X射线的波长λ为0.6199 Å。在正式测试前,选用CeO2作为标准样品进行仪器参数校正。通过TOPAS[27]对XRD谱进行精修,得到随压力变化的材料晶胞参数等结构信息。
图3(a)所示,能量色散谱(energy dispersive spectroscopy,EDS)分析发现,单晶样品中La、Zn、Sb元素的实际原子比为1∶0.72∶2,证实了Zn位缺陷的存在,与之前的文献报道[2123]相一致。为了确认Zn含量的均匀性,对多块独立生长的单晶样品进行了EDS分析。结果显示,不同样品的实际Zn含量均为0.72左右,表明本研究的样品中Zn缺陷浓度具有很好的均一性。图3(b)为常压下LaZn1–δSb2单晶的XRD谱。可见,只有(00l)方向的衍射峰被观测到,表明合成的LaZn1–δSb2单晶具有c轴单一取向。为了研究LaZn1–δSb2在常压下的磁性,在1 T外加磁场下测量了样品的磁化率χ随温度T的变化曲线,如图3(c)所示。可以看到,在所测试的温度范围内(2~300 K),磁化率随着温度的降低呈现逐渐上升趋势。需要注意的是,本研究中LaZn1–δSb2单晶的磁化行为与之前的报道[23]略有差别,即样品表现出更强的温度依赖性,可能源于Zn缺位的减少。Zn含量的变化可能改变了材料的电子能带结构,导致费米面附近的电子态密度发生变化;或者引入了微弱的局域磁矩交换作用,从而增强了磁化率对温度的敏感性。根据居里-外斯(Curie-Weiss)定律$ \chi \left(T\right)={\chi }_{0}+C/ \left(T-{T}_{\theta }\right) $,可拟合得到磁化率-温度(χ-T)曲线,其中:$ {\chi }_{0} $为温度趋近于无穷时的磁化率,代表磁化率中与温度无关的项;$ C $为居里常数,与材料的有效磁矩($ {\mu }_{\text{eff}} $)相关;$ {T}_{\theta } $为磁相互作用的特征温度,其值的正负与材料的磁性类型相关。拟合结果表明,LaZn1–δSb2样品在全温区内表现为理想顺磁性,有效磁矩较小,约为0.22 $ {\mu }_{\text{B}} $/(f.u.)。
图4(a) 展示了电流平行和垂直于ab面的归一化电阻率-温度(ρ/ρ300 K-T)曲线,可以看出,电流沿ab面的输运表现出更典型的金属性行为(剩余电阻率比ρ300 K/ρ2 K=12.3,其中ρ300 Kρ2 K分别为300和2 K时的电阻率),电阻率随温度降低而单调下降。相比之下,电流垂直于ab面的电阻率在整个温区都显著高于面内方向,且剩余电阻率比更小(4.9),表明LaZn1–δSb2在电输运性质上存在一定的各向异性。这种各向异性通常与材料的层状晶体结构有关,说明面内的电子耦合强度高于层间耦合。图4(b)为不同温度下样品的磁阻测试结果,磁阻计算公式通常为$ {M}_{R}=\left[R\left(H\right)-R\left(0\right)\right]/R(0) $,其中:$ R(H) $为磁场H下的电阻,$ R(0) $为零场电阻。在所有测量温度下,LaZn1–δSb2均表现出正磁阻,且磁阻随磁场增加呈线性增长趋势,尤其是在低温下,磁阻的大小表现出强烈的温度依赖性,且该依赖性随着温度的升高而迅速减弱。LaZn1–δSb2的霍尔电阻率$ {\rho }_{xy} $同样呈现线性的磁场依赖关系,如图4(c)所示。LaZn1–δSb2的霍尔电阻率在低温下为正值,随着温度的升高,缓慢变为负值,表明材料中主导的载流子类型从空穴型逐渐转变为电子型。图4(d)显示了通过公式$ {R}_{\rm H}={\rho }_{xy}/B $计算得到的霍尔系数$ {R}_{\rm H} $随温度的变化关系(电流I= 1 mA),可以看到,霍尔系数随温度的依赖性很强,表明LaZn1–δSb2可能是一个多带体系[28]
为了揭示LaZn1–δSb2在高压下的结构演变规律,进行了原位高压同步辐射XRD测量。图5(a)为不同压力下LaZn1–δSb2的同步辐射XRD谱。可以看出,直到最高压力52.6 GPa,所有衍射峰均向高角度方向缓慢移动,没有出现新的衍射峰,表明样品始终维持初始的四方P4/nmm空间群。压力下部分衍射峰发生展宽和强度减弱是高压结构测量中的普遍现象,可能与材料在压力下晶粒发生细化或择优排列有关。为了更好地分析LaZn1–δSb2在高压下的晶胞参数变化,绘制了晶格常数(ac)随压力(p)的变化曲线,如图5(b)所示。高压下LaZn1–δSb2的晶格常数随着压力的升高逐渐减小,c轴的压缩相较于ab面更为剧烈,但是没有出现突变。图5(c) 展示了高压下LaZn1–δSb2的晶胞体积(V)随压力的变化。可见,V随压力的增加呈现连续、平滑减小趋势,52.6 GPa下的晶胞体积相较于常压下减小约25%。LaZn1–δSb2的晶胞体积随压力的依赖性可以用三阶Birch-Murnaghan(B-M)方程[29]拟合,即
$ p(V)=\frac{3}{2}{B}_{0}\left[\left(\frac{{V}_{0}}{V}\right)^{7/3}-\left(\frac{{V}_{0}}{V}\right)^{5/3}\right]\left\{1+\frac{3}{4}(B'_{0}-4)\left[\left(\frac{{V}_{0}}{V}\right)^{2/3}-1\right]\right\} $
式中:V0B0$B'_{0} $分别为零压下的晶胞体积、体积模量以及体积模量对压力的一阶导数。LaZn1–δSb2的晶胞体积随压力的拟合结果为:V0=201.21 Å3B0=82.46 GPa,$B'_{0} $=4.08。实验数据与拟合曲线之间的良好一致性表明,在所测量的压力范围内,LaZn1–δSb2的晶胞体积被连续地压缩。当压力超过40 GPa时,XRD峰出现显著展宽,部分衍射峰的强度减弱,这主要源于高压下传压介质的应力增加,从而引入位错或导致晶粒破碎。尽管存在展宽,但是所有衍射峰均可由同一空间群指标化,且晶胞体积随压力变化平滑,未发现存在一级结构相变的证据。图6(a)图6(b)分别展示了在2.7和52.6 GPa 压力下测量得到的XRD谱及其结构精修结果,所有衍射峰均可通过四方结构的LaZn1–δSb2得到较好的拟合。图6中实验曲线与拟合曲线的一致性较好(加权图形剩余方差因子Rwp为3.3%和5.2%),进一步证明材料在压力下没有发生结构相变。
为研究压力对LaZn1–δSb2输运性质的调控,利用DAC开展了最高压力为50.9 GPa的电输运测量,结果如图7(a)图7(b)所示。需要说明的是,由于高压下的电阻测量不是标准的四电极法,因此,在高压输运测量结果中直接展示电阻值,而没有转化为电阻率。从图7(a)图7(b)中可以看出:在0.8~30.6 GPa压力区间内,电阻随温度降低整体呈下降趋势,且压力越大,室温电阻越低;当压力超过35.4 GPa 后,电阻随温度变化的趋势保持金属性行为不变,但室温电阻随压力的升高而反常增加,可能与压力导致的晶格散射增强有关[3031]。在低压区,散射可能主要源于声子或杂质;而在高压条件下,晶体结构压缩或能带重构可能导致散射强度增强,电子-电子散射或由局域磁矩涨落引起的散射可能成为主导,进而引起绝对电阻值增大。此外,对于自旋-轨道耦合比较强的材料,高压导致的晶格畸变效应比压力诱导的能带展宽效应更具优势,也可能造成电阻在压力下的反常增加。为了更清晰地展示电阻-温度依赖行为随压力的变化,以样品在300 K时的电阻R300 K为基准,将不同压力下的电阻-温度曲线进行归一化,如图7(c)所示,可以看到,材料的归一化电阻R/R300 K曲线同样与压力存在非线性关系。图7(c)中的插图给出了R300 K/R2 K随压力的变化。R300 K/R2 K随压力升高先逐渐减小,后基本保持不变,并有微弱上升趋势。在低于30 GPa 的压力范围内,R300 K/R2 K的下降可能源于电子-声子散射被抑制或杂质散射增强;而在高压区域,R300 K/R2 K的饱和则说明散射机制趋于稳定,材料的本征电子输运特性逐渐占主导。为了进一步分析压力下LaZn1–δSb2的输运行为变化,使用$ R (T)=R_{0}+A{T}^{n} $对2~50 K范围内电阻的温度依赖行为进行拟合(A为拟合参数,n为温度幂指数,R0为绝对零度时的电阻),得到n随压力的变化关系,如图7(d)所示。从图7(d)可以看出,n从低压下的约2.3逐渐上升至高压下的2.8左右,并最终趋于平稳。该结果符合传统金属的电子输运模型,n的增大反映了电子-声子散射在输运过程中的权重增加;而其在高压下的饱和则表明压力对散射机制的调控存在阈值,可能与能带填充极限有关。压力下幂指数n的变化可能源于压力诱导的声子谱硬化或费米面结构和费米能级附近电子态密度的变化。高压通常导致声子频率整体上移,可能改变电子-声子散射的相空间以及散射率对温度的函数关系。同时,压力也可能改变能带结构,影响费米面的形状和费米能级附近的电子态密度,也可能改变散射率与温度的依赖关系。
在本研究中,在最高达50.9 GPa的压力范围内,没有发现LaZn1–δSb2有高于2 K的超导现象。分析认为,其原因可能有以下几点。首先,考虑到ReTSb2系列化合物中超导体的Tc普遍偏低,LaZn1–δSb2中可能已经发生了2 K以下的超导,只是没有被探测到。在后续工作中,可以将温度降至更低来探测材料中可能的超导电性。其次,材料化学组分研究发现,LaZn1–δSb2中存在大量的Zn位缺陷。由于Zn是组成Zn-Sb准二维导电层的关键部分,因此,Zn位缺陷会对材料的输运行为产生非常显著的影响。为了进一步探索LaZn1–δSb2中可能的超导电性,降低Zn位缺陷应该非常重要。在后续工作中,计划通过La位的元素替代,如引入Sr2+和Ca2+等空穴掺杂,尝试减少Zn位的位置缺陷。从化学元素价态平衡的角度来考虑,这应该是可行的,因为更多的空穴掺杂可以部分替代或抑制材料母体中本征Zn位缺陷行为。此外,利用高温高压合成等极端条件,也可能更容易合成出标准化学计量比的LaZnSb2目标产物。最后,进一步提高测试压力,有可能在特定压力下诱导晶体结构/电子结构突变,从而得到新的超导电性。
本研究成功制备了锌基112型化合物LaZn1–δSb2的高质量单晶样品,系统研究了其晶体结构、化学成分以及在常压和高压条件下的结构和低温输运行为的演变规律。常压表征表明,该材料表现为顺磁金属,且存在一定的各向异性;霍尔系数随温度显著变化,符合多带输运模型特征。高压同步辐射XRD结果表明,在高达52.6 GPa的压力范围内,LaZn1–δSb2始终保持与常压下一致的四方结构,未发生结构相变。压力下的电输运测量发现,高压可以逐渐调制其低温电输运行为。LaZn1–δSb2在压力下的输运依然由电子-声子散射主导,且散射指数随压力逐渐升高,后逐渐趋于饱和。在最高达50.9 GPa的压力下,未观测到2 K以上的超导转变。分析认为,LaZn1–δSb2超导态的缺失可能与材料中固有的Zn空位所引起的晶格无序及对电子态的调制有关。
LaZn1–δSb2作为一种典型的具有Zn-Sb准二维层的112型化合物,其晶体结构中存在本征的Zn位缺陷,这种结构缺陷对材料的电子性质和输运行为产生重要影响。研究该材料在高压条件下的结构演化和物性变化,不仅有助于理解层状化合物的基本物理性质,也为探索高压诱导的可能的新型量子态提供了重要线索。特别是在当前的高温超导研究热潮中,理解压力对特定结构材料的电子关联强度和晶格动力学的影响具有重要的物理意义。
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2026年第40卷第4期
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doi: 10.11858/gywlxb.20261005
  • 接收时间:2026-01-08
  • 首发时间:2026-04-29
  • 出版时间:2026-04-05
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  • 收稿日期:2026-01-08
  • 修回日期:2026-02-08
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    南京大学物理学院超导物理与材料研究中心, 江苏 南京 210093

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李 庆(1991-),男,博士,助理教授,主要从事新型超导材料探索和压力下的性质调控研究. E-mail:
闻海虎(1964-),男,博士,教授,主要从事新型超导材料的探索合成、高温超导材料的超导机理和超导体磁通动力学研究. E-mail:
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2种不同金属材料的力学参数

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种数
Number of
species
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species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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