大尺寸黑磷晶体的制备  

Synthesis of Large-Size Black Phosphorus Crystals

作　　者：刘豪哲 郭江涛 王琴 杨培志[1] Liu Haozhe;Guo Jiangtao;Wang Qin;Yang Peizhi(Key Laboratory of Advanced Technique&Preparation for Renewable Energy Materials,Ministry of Education,Yunnan Normal University,Kunming 650500,Yunnan,China)

机构地区：[1]云南师范大学可再生能源材料先进技术与制备教育部重点实验室,云南昆明650500

出　　处：《光学学报》2024年第13期191-198,共8页Acta Optica Sinica

基　　金：国家自然科学基金(U1802257,12264057);云南省基础研究重点基金(202201AS070023);“兴滇英才支持计划”“春城计划”高层次人才引进培养工程(2022SCP005)。

摘　　要：黑磷(BP)具有可调控的带隙、高载流子迁移率、优良的通断比和热导率等特性,然而目前常用的制备BP的方法化学气相运输(CVT)法可能会引入杂质,且仅依靠CVT法难以获得高质量且大尺寸的BP晶体。本研究结合CVT法和种晶法,通过改变籽晶的数量,研究高质量、大尺寸BP的生长方法,并对BP的晶体结构、结晶质量、晶体形貌、光学性质和电学性质进行表征和分析。结果表明,在采用CVT法制备BP晶体的过程中引入BP籽晶,于595℃的真空环境中退火6 h,最终获得的BP晶体的横向尺寸是原始BP的1.5倍,这为制备高质量、大尺寸BP晶体提供了有益参考。Objective Black phosphorus(BP) is widely applied to semiconductor technology, optoelectronics, field-effect transistors, and flexible electronic devices due to its tunable bandgap, high carrier mobility, excellent switching ratio, and perfect thermal conductivity. As an allotrope of phosphorus, BP has a layered structure and is more stable than white phosphorus(WP) and red phosphorus(RP). Currently, the primary method for synthesizing BP is chemical vapor transport(CVT). The CVT method has strong controllability and the ability to synthesize multiple materials and is thus widely employed in the synthesis of semiconductor materials and the manufacturing of optoelectronic devices. Although the orthogonal BP preparation is relatively mature, the CVT method introduces mineralizers, which results in the presence of impurities in the synthesized BP. These impurities may affect the performance and application of BP. Therefore, further purification processes are needed. We combine the CVT method with seed crystal technology to investigate the growth of high-quality and large-size BP.Methods The high-quality and large-size BP is successfully prepared by changing the seed crystal number. The specific experimental steps are as follows. RP, Sn, and SnI4 are weighed at a ratio of 50∶2∶1 in a glove box to prepare the experimental materials, followed by vacuum sealing. The sealed quartz tube is horizontally placed in a muffle furnace and heated at around 620 ℃. The temperature is maintained for five hours to completely melt RP, then slowly drops to 500 ℃within six hours, and is maintained at 500 ℃ for six hours. The rise and fall programs of the temperature are ended when the temperature slowly lowers to 450 ℃. After the muffle furnace is cooled to room temperature, the quartz tube is removed. Then the obtained BP crystals are cleaned by ultrasonic treatment with anhydrous ethanol and then dried in a vacuum drying oven. A small piece of dried BP with a flat size of 0.5 mm×0.2 mm is adopted as the seed crystal.Subse

关 键 词：材料 化学气相运输法 种晶法 正交黑磷 大尺寸 

分 类 号：TB321[一般工业技术—材料科学与工程]