固态溴素合成溴化物晶体的研究——以CrSBr合成和表征为例

doi:10.6023/A24090276

摘要/Abstract

CrSBr是一种磁性二维材料, 因其独特的磁学、电学和光学特性而受到越来越多的关注. 然而, CrSBr晶体的传统合成方法都需要以液溴作为原料, 而液溴具有挥发性、毒性和腐蚀性, 为CrSBr晶体的合成带来了不便与危险. 为了解决该问题, 本工作在尝试多种溴素储存晶体后, 选择具有化学固溴性能的Cs₄Sb₂Br₁₂化合物作为新溴源, 取代液溴, 成功合成了CrSBr晶体. 通过X射线衍射(XRD)、光致发光(PL)和拉曼(Raman)光谱等手段对合成的CrSBr晶体进行了表征. 本工作开发的固态溴素合成法, 为CrSBr晶体的合成提供了更好的安全性, 也为其他固态卤素在晶体合成中的应用提供了新的思路.

关键词: 二维材料, 化学气相传输法, 晶体生长, 固态溴素, 铬硫溴

CrSBr, a magnetic two-dimensional material, has attracted increasing attention for its unique magnetic, electronic, and optical properties. Elemental bromine is necessary for the synthesis of CrSBr crystals in the previous reports. However, elemental bromine is a kind of chemical, which is volatile, highly toxic, and corrosive liquid at room temperature. The use of elemental bromine complicates the synthesis process and elevates safety risks in the laboratory. Herein, we report a novel method for the synthesis of CrSBr using solid-state bromine Cs₄Sb₂Br₁₂ as a new bromine source instead of liquid bromine, circumventing the associated inconveniences and hazards. Typical synthesis conditions for CrSBr are as follows: Cs₄Sb₂Br₁₂ crystals (0.50 mmol, 1.0 equiv.) are placed at the left end of a 24 cm quartz tube, with chromium powder (1.00 mmol, 2.0 equiv.) and sulfur powder (1.00 mmol, 2.0 equiv.) positioned at the right end. The tube is then sealed under vacuum with a necked middle part. The necked part is used to prevent premature mixing of the reactants. Thereafter, the evacuated quartz tube is placed in a two-zone tubular furnace. The material undergoes a pre-reaction at 250 ℃ for 24 h to completely release bromine. Subsequently, while the left end is maintained at a constant temperature of 250 ℃, the right end is heated to 700 ℃ in 8 h and stays there for 12 h, then increased to 880 ℃ in 3 h, and gradually raised to 930 ℃ over a period of 5 d. Finally, the temperature is slowly reduced to room temperature over the course of one day. After cooling, the high-quality CrSBr single crystals are collected and comprehensively characterized by X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and Raman spectroscopy techniques. Compared to traditional methods, the solid-state bromine synthesis of CrSBr not only circumvents the potential hazards associated with the direct use of bromine, enhancing the safety of the synthesis process, but also provides a novel approach for the application of other solid-state halogens in crystal synthesis.

Key words: two-dimensional materials, chemical vapor transport method, crystal growth, solid-state bromine, CrSBr

引用此文

许木榕, 周纯, 王子慧, 杨丽冰, 李晨远, 卓炜丰, 王行之, 杜克钊. 固态溴素合成溴化物晶体的研究——以CrSBr合成和表征为例[J]. 化学学报, 2024, 82(12): 1234-1240.

Murong Xu, Chun Zhou, Zihui Wang, Libing Yang, Chenyuan Li, Weifeng Zhuo, Xingzhi Wang, Kezhao Du. Solid-State Bromine for Bromide Synthesis, a Case Study of CrSBr[J]. Acta Chimica Sinica, 2024, 82(12): 1234-1240.

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图/表 7

序号	溴源	管子长度	条件^a	实验结果	是否成功	备注
1	Cs₄Sb₂Br₁₂	24 cm	溴源端分开	CrSBr	√	针状黑色晶体产出
2	Cs₄Sb₂Br₁₂	10 cm	溴源端分开	Cr_0.67S	×	两端温差为100 ℃, 不利于CrSBr合成
3	Cs₄Sb₂Br₁₂	24 cm	溴源端未分开	Cr_0.67S	×	无法较好释放溴素
4	KBrO₃+KBr	24 cm	溴源端未分开	爆管	×	原料对石英管具有一定腐蚀性
5	KBrO₃+KBr	24 cm	溴源端未分开, 镀膜^b	Cr₂O₃	×	KBrO₃高温分解, 提供溴源不稳定
6	CsBr₃	—	溴源端未分开	—	×	CsBr₃不稳定, 未封管已变为白色CsBr
7	C₁₆H₃₆NBr₃	13 cm	溴源端未分开	爆管	×	有机物碳化, 导致气压上升

表1. 本工作尝试的固态溴源及结果

Table 1. Solid-state bromine sources attempted in this work and their results

图1. 合成方法介绍. (a)固态溴素合成CrSBr装置示意图. (b)本方法温度控制曲线. (c) CrSBr的光学显微照片. (d)反应结束后样管照片

Figure 1. Introduction to the synthesis method. (a) Schematic diagram of the CrSBr synthesis apparatus. (b) The temperature control curve of this method. (c) Optical micrograph of CrSBr. (d) Photograph of the sample tube after the reaction is completed

图2. Syn-CrSBr、放置6个月的Syn-CrSBr与CrSBr标准卡片的PXRD数据对比图

Figure 2. Comparison of PXRD data of Syn-CrSBr, aged Syn-CrSBr for six months and the standard card of CrSBr

图3. Syn-CrSBr和Com-CrSBr的光致发光光谱图. (a)市售CrSBr组随机抽取样品光学照片. (b)、(c)、(d)本方法合成CrSBr组随机抽取样品光学照片. (e) Com-CrSBr不同点位PL对比. (f) Syn-CrSBr不同点位PL对比. (g) Syn-CrSBr-1和Com-CrSBr-1 PL对比

Figure 3. Photoluminescence (PL) spectra of Syn-CrSBr and Com-CrSBr. (a) Optical micrograph of a randomly selected sample of commercial CrSBr. (b), (c), (d) Optical micrographs of randomly selected samples of CrSBr synthesized by the method presented in this work. (e) Comparison of photoluminescence at different points for Com-CrSBr. (f) Comparison of photoluminescence at different points for Syn-CrSBr. (g) Comparison of photoluminescence for Syn-CrSBr-1 and Com-CrSBr-1

图4. 拉曼光谱. (a) Syn-CrSBr不同点位和Com-CrSBr的拉曼光谱对比. (b)图4c和4d测试所用的Syn-CrSBr晶体照片. (c)激光分别沿a轴和b轴激发测量的Syn-CrSBr拉曼光谱, 显示面外A1 g模式约114 cm-1、A2 g模式约244 cm-1和 A3 g模式约344 cm-1, 以及微弱的B1 2g模式约92 cm-1、B2 2g模式约194 cm-1、B3 2g模式约301 cm-1. (d)激光分别沿c轴和与c轴有一定角度的方向激发测量的Syn-CrSBr拉曼光谱(E表示激光入射方向, a和b分别表示样品面内的a和b轴方向, c表示垂直样品面外的c轴方向, θ表示激光与c轴的夹角)

Figure 4. Raman spectra. (a) Raman spectra comparison between Com-CrSBr and different points of Syn-CrSBr. (b) Optical photograph of Syn-CrSBr sample for the measurement in Figure 4c and 4d. (c) Raman spectra of Syn-CrSBr excited by the laser along the a-axis and b-axis, respectively, showing out-of-plane A1 g mode ca. 114 cm-1, A2 g mode ca. 244 cm-1, and A3 g mode ca. 344 cm-1, as well as weak B1 2g mode ca. 92 cm-1, B2 2g mode ca. 194 cm-1, and B3 2g mode ca. 301 cm-1. (d) Raman spectra of Syn-CrSBr excited by the laser along the c-axis and the direction offset by a certain angle along the c-axis, respectively (E represents the direction of laser incidence. a and b represent the a-axis and b-axis in-plane, respectively. c represents the c-axis perpendicular to the sample surface. θ represents the angle between the laser and c-axis)

图5. 低温光致发光谱图. (a)本组测试所用的Syn-CrSBr样品照片. (b) Syn-CrSBr在8 K下的光致发光谱图. (c) Syn-CrSBr在8 K下的变功率光致发光谱图. (d) 8 K时, A、B、C和D峰的强度与激发功率的关系图. (e) 8 K时, F、G、H和I峰的强度与激发功率的关系图. (f) Syn-CrSBr的变温光致发光谱图

Figure 5. Low-temperature PL spectra. (a) Optical photograph of Syn-CrSBr sample for measurement in this group. (b) PL spectrum of Syn-CrSBr at 8 K. (c) Excitation power dependent-PL spectra of Syn-CrSBr at 8 K. (d) The relationship between the excitation power and the PL intensity of peaks A, B, C and D at 8 K. (e) The relationship between the excitation power and the PL intensity of peaks F, G, H and I at 8 K. (f) Temperature-dependent PL spectra of Syn-CrSBr

试剂名称	化学式	纯度	生产厂家
溴化铯三氧化二锑溴酸钾氢溴酸铬硫	CsBr Sb₂O₃ KBrO₃ HBr Cr S	99.9% 99% 99% 40%~48% 99.95% 99.99%	Adamas Acros Aladdin Aladdin Adamas Adamas

表2. 化学试剂信息

Table 2. Chemical reagent information

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