Solid-State Bromine for Bromide Synthesis, a Case Study of CrSBr

doi:10.6023/A24090276

Abstract

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

Cite this article

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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Fig. & Tab. 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

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

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

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

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

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)

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

Table 2. Chemical reagent information

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固态溴素合成溴化物晶体的研究——以CrSBr合成和表征为例