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Single crystal growth of topological semimetals and magnetic topological materials

Wang Huan He Chun-Juan Xu Sheng Wang Yi-Yan Zeng Xiang-Yu Lin Jun-Fa Wang Xiao-Yan Gong Jing Ma Xiao-Ping Han Kun Wang Yi-Ting Xia Tian-Long

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Single crystal growth of topological semimetals and magnetic topological materials

Wang Huan, He Chun-Juan, Xu Sheng, Wang Yi-Yan, Zeng Xiang-Yu, Lin Jun-Fa, Wang Xiao-Yan, Gong Jing, Ma Xiao-Ping, Han Kun, Wang Yi-Ting, Xia Tian-Long
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  • Topological materials have attracted much attention due to their novel physical properties. These materials can not only serve as a platform for studying the fundamental physics, but also demonstrate a significant potential application in electronics, and they are studied usually in two ways. One is to constantly explore new experimental phenomena and physical problems in existing topological materials, and the other is to predict and discover new topological material systems and carry out synthesis for further studies. In a word, high-quality crystals are very important for studying quantum oscillations, angle resolved photoemission spectra or scanning tunneling microscopy. In this work, the classifications and developments of topological materials, including topological insulators, topological semimetals, and magnetic topological materials, are introduced. As usually employed growth methods in growing topological materials, flux and vapour transport methods are introduced in detail. Other growth methods, such as Bridgman, float-zone, vapour deposition and molecular beam epitaxy methods, are also briefly mentioned. Then the details about the crystal growth of some typical topological materials, including topological insulators/semimetals, high Chern number chiral topological semimetals and magnetic topological materials, are elaborated. Meanwhile, the identification of crystal quality is also briefly introduced, including the analysis of crystal composition and structure, which are greatly important.
      Corresponding author: Xia Tian-Long, tlxia@ruc.edu.cn
    • Funds: Project supported by the National Key R&D Program of China (Grant No. 2019YFA0308602), the National Natural Science Foundation of China (Grant Nos. 12074425, 11874422), the Fundamental Research Fund for the Central Universities, China (Grant Nos. 18XNLG14, 19XNLG18), and the Outstanding Innovative Talents Cultivation Funded Programs 2020 of Renmin University of China
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  • 图 1  Ba-Ga元素二元相图[143], 其中插图为自助溶方法生长的BaGa2及BaGa4单晶

    Figure 1.  Ba-Ga binary phase diagram. Insets are typical grown single crystal of BaGa2 and BaGa4, respectively

    图 2  Pt-Bi元素二元相图[148], 其中插图为所生长的不同结构的PtBi2单晶

    Figure 2.  Pt-Bi binary phase diagram. Insets are typical grown single crystal of PtBi2 with different structures

    图 3  (a) 常用石英管类型; (b) 常用石英堵头与坩埚类型; (c) 封管后的样品离心前后对比示意图

    Figure 3.  (a) Different types of quartz tube frequently used; (b) different types of quartz plug and crucible frequently used; (c) sealed sample before and after centrifugation

    图 4  物理气相输运以及化学气相输运过程示意图, 以(T(S) > T(C)) 为例

    Figure 4.  Physical vapour transport and chemical vapour transport. Take the case (T(S) > T(C)) as an example

    图 5  Pd-Te元素二元相图[156], 插图为生长出的PdTe2单晶

    Figure 5.  Pd-Te binary phase diagram. Inset is the typical grown single crystal of PdTe2

    图 6  (a) Cd-As元素二元相图[164]; (b) 助溶剂方法生长出的单晶; (c) 气相输运方法生长的单晶

    Figure 6.  (a) Cd-As binary phase diagram; (b) the single crystal grown from the flux method; (c) the single crystal grown from the vapour transport method

    图 7  通过气相输运方法得到的(a) NbAs2和(b) TaAs2单晶样品

    Figure 7.  Single crystals of (a) NbAs2 and (b) TaAs2 grown from the vapour transport method

    图 8  助溶剂方法生长出的(a) RuAs2, (b) IrAs2, (c) CoAs2单晶

    Figure 8.  Single crystals of (a) RuAs2, (b) IrAs2 and (c) CoAs2 grown by flux method

    图 9  (a) YSb, (b) TmSb, (c) HoSb, (d) DyBi单晶图片

    Figure 9.  Photos of single crystal (a) YSb, (b) TmSb, (c) HoSb and (d) DyBi

    图 10  (a) Co-Te[177]和(b) Si-Te[178]二元相图; (c), (d) 通过化学气相输运方法得到的CoSi单晶; (e) 助溶剂方法生长的CoSi单晶

    Figure 10.  Binary phase diagram of (a) Co-Te[177] and (b) Si-Te[178]. The single crystal of CoSi grown from the vapour transport (c), (d) and flux method (e)

    图 11  (a) Co-Sb[179], (b) Sb-Si[180], (c) Co-Sn[181] 与(d) Si-Sn[182]元素二元相图. (b)中插图与 (d)中插图分别为用Sb和Sn作为助溶剂生长的CoSi单晶

    Figure 11.  (a) Co-Sb[179], (b) Sb-Si[180], (c) Co-Sn[181] and (d) Si-Sn[182] binary phase diagram. Insets in panels (b) and (d) are the single crystal of CoSi grown from the Sb and Sn flux

    图 12  (a) Bi-Rh[183]及(b) Bi-Sn[184]元素的二元相图, 插图为典型的RhSn单晶; (c) 同一块单晶中不同晶面的单晶XRD衍射图谱

    Figure 12.  (a) Bi-Rh[183] and (b) Bi-Sn[184] binary phase diagram. Inset is the single crystal of RhSn grown from flux method. (c) Single-crystal XRD pattern of RhSn with different crystal faces

    图 13  (a) Bi-Pt[148]以及(b) Bi-Ga[185]元素的二元相图, 插图为助溶剂方法生长出的PtGa单晶

    Figure 13.  (a) Pt-Bi[148] and (b) Bi-Ga[185] binary phase diagram. Insets are the single crystals of PtGa grown from flux method

    图 14  (a) Bi-Pd[186]以及(b) Bi-Ga[185]元素的二元相图; (c), (d) 不同晶面的单晶XRD衍射图谱

    Figure 14.  (a) Bi-Pd[186] and (b) Bi-Ga[185] binary phase diagram; (c), (d) single-crystal XRD patterns of PdGa with different crystal faces

    图 15  (a) YbMnSb2与 (b) EuMnSb2单晶照片及单晶X射线衍射谱图

    Figure 15.  Photos and XRD sprctras of single crystal (a) YbMnSb2 and (b) EuMnSb2

    图 16  (a) Al-Eu[200]以及(b) Al-B[201]元素二元相图; (c), (d) 典型的EuB6单晶样品

    Figure 16.  (a) Al-Eu[200] and (b) Al-B[201] binary phase diagram; (c), (d) typical grown single crystals of EuB6

    图 17  (a) Al-Sm[203]以及(b) Al-B[201]元素二元相图, 插图为典型的SmB6单晶样品

    Figure 17.  (a) Al-Sm[203] and (b) Al-B[201] binary phase diagram. Insets are typical grown single crystals of SmB6

    图 18  (a) Co3Sn2S2与 (b) Co3In2S2单晶样品

    Figure 18.  Single crystals of (a) Co3Sn2S2 and (b) Co3In2S2

    图 19  (a) Fe-Sn[209]元素二元相图, 插图为自助溶剂方法生长的Fe3Sn2单晶样品; (b) 气相输运方法生长的Fe3Sn2单晶样品

    Figure 19.  (a) Fe-Sn[209] binary phase diagram. Inset is the single crystal of Fe3Sn2 grown from the flux method. (b) The single crystals grown from the vapour transport

    图 20  (a) MnBi2Te4, (b) MnBi4Te7, (c) MnBi6Te10与(d) MnBi8Te13的晶体图以及相应的单晶X射线衍射图谱

    Figure 20.  Single-crystal XRD patterns of (a) MnBi2Te4, (b) MnBi4Te7, (c) MnBi6Te10 and (d) MnBi8Te13. Insets are corresponding photos of single crystals

    图 21  (a) Eu-In[229]元素二元相图; (b) As-In[230]元素二元相图, 其中插图为生长的EuIn2As2单晶

    Figure 21.  (a) Eu-In[229] and (b) As-In[230] binary phase diagram. Inset is the grown single crystals

    表 1  常用的金属助溶剂性质

    Table 1.  Properties of the frequently-used fluxes.

    熔点/℃ 沸点/℃ 可溶于酸或碱溶液 密度/(g·cm-3) 毒性
    Al 660.3 2327 硫酸/硝酸/盐酸/氢氧化钠/氢氧化钾 2.70
    Ga 29.8 2400 盐酸/硫酸 5.90
    In 156.6 2000 硝酸/盐酸/硫酸 7.31
    Sn 231.9 2270 盐酸/硝酸/碱溶液 7.28
    Pb 327.5 1740 硫酸/硝酸/有机酸溶液/碱溶液 11.34
    Sb 630.6 1635 硫酸 6.69
    Bi 271.3 1500 硝酸 9.78
    Te 449.5 989.8 硝酸/盐酸/氢氧化钾 6.24
    Cd 321.2 765 盐酸 8.65
    DownLoad: CSV

    表 2  常用的输运剂性质

    Table 2.  Properties of the frequently-used transport agents

    熔点/℃ 沸点/℃ 稳定性 可溶于溶液 形貌 储存
    I2 113 184 易挥发/易升华 乙醇 紫红色颗粒 密封干燥
    TeCl4 224 380 易潮解 水/盐酸 白色粉末 密封干燥
    BiCl3 230 447 易潮解 水/盐酸 白色粉末 密封干燥
    BiBr3 218 441 易潮解 水/稀盐酸/丙酮 黄色粉末 密封干燥
    TeBr4 380 420 易潮解 水/氢氧化钠 黄色粉末 避光/密封
    SnI4 144.5 364 / 乙醇 橘黄色粉末 密封干燥
    TeI4 280 118 (升华点) 灼热易分解 乙醇/丙酮 灰色粉末 密封干燥
    DownLoad: CSV

    表 3  不同生长方法的优缺点及适用范围

    Table 3.  Advantages and disadvantages of different growth methods and their application scope

    优点 缺点 适用范围
    熔融重结晶法 1. 不需要加入其他试剂如助溶剂或输运剂, 损耗少且不引入杂质;
    2. 不需要额外处理其他溶剂的分离或回收, 操作简单.
    适用性不强 适合生长具有低熔点的目标材料
    助溶
    剂法
    1. 适用性强, 几乎对于所有材料只要找到合适的助溶剂都可以将其以单晶形式生长出来;
    2. 生长温度低, 适合熔点很高的化合物;
    3. 生长出的晶体均匀完整.
    1. 生长周期长;
    2. 许多助溶剂都有不同程度的毒性 处理后的助溶剂或含有助溶剂的溶液具有腐蚀性还会产生污染, 要做好分类并小心处理;
    3. 使用坩埚, 可能会影响品体成核与生长取向.
    适合生长本身熔点较高的化合物
    气相输运法 1. 可以实现常压下难以合成的化合物;
    2. 可以合成难以通过固-固, 固-液反应合成的化合物;
    3. 温度调节灵活, 可以直接调控晶体生长时所需的应力, 饱和度等参量, 进而影响晶体的生长速度.
    1. 产量较低;
    2. 需要精准掌控输运剂的浓度和低沸点反应物的总量, 否则容易因为管内压强过大造成爆管;
    3. 有些气相输运法需要通惰性气体或氢气, 操作复杂, 有一定的危险;
    4. 管壁会限制晶体生长方向, 与管壁接触的晶面呈曲面.
    适合生长反应物中沸点较低的化合物或其它难以通过固-固、固-液合成的化合物
    DownLoad: CSV
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Metrics
  • Abstract views:  11695
  • PDF Downloads:  450
  • Cited By: 0
Publishing process
  • Received Date:  04 August 2022
  • Accepted Date:  04 November 2022
  • Available Online:  16 January 2023
  • Published Online:  05 February 2023

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