Zhang Leilei, Cui Shuangyue, Guo Qing, Ge Chao, Han Quanxiang, Lin Qinglian, Li Cuicui, Zheng Xiaoxin, Zhai Zhongjun, Wang Lei, Sun Qihao, Xu Yadong, Liu Yang, Tao Xutang
State Key Laboratory of Crystal Materials, Shandong University, Jinan, Shandong 250100, P. R. China.
ACS Appl Mater Interfaces. 2020 Nov 18;12(46):51616-51627. doi: 10.1021/acsami.0c14582. Epub 2020 Nov 9.
It has been proved that bulk single crystals of a halide perovskite behave much better than its polycrystalline counterparts in multiple application scenarios. Thus, the growth of large-sized and high-quality single crystals is significant to guarantee their ultimate device performances. Here, based on our recently invented settled temperature and controlled antisolvent diffusion system, improvements achieved in this work include the following: (1) We modified the growth system to optimize the control over both mass and heat transport to alleviate defect formation. State-of-the-art-quality MAPbBr crystals were grown, and from the bulk crystals, differently oriented crystalline wafers were fabricated with the full width at half-maximum of X-ray rocking curves of 40-86 arcsec. (2) The optical band gaps revealed no anisotropy on differently oriented wafers, whereas the refractive index and extinction coefficient exhibited obvious anisotropy. (3) Angle-resolved polarized Raman spectra demonstrate distinct in-plane anisotropy on (100) and (110) wafers but not on the (111) wafer. The equilibrium MA orientations are deduced to adopt the <111> direction with the antiparallel MA orientation between adjacent domains. (4) Radiation detectors fabricated on differently oriented wafers proved photoresponse anisotropy to both visible and X-ray radiation, following a general order of (100) > (110) > (111). Because anisotropy is an inevitable issue for various applications employing crystalline materials, this study, based on the clarification of the debatable intrinsic dipole configuration in the pseudocubic crystal lattice, will provide quantitative information on physicochemical property anisotropy and subsequently facilitate optimization of device performance referring to crystal orientations of halide perovskite crystals.
已证明,卤化物钙钛矿的块状单晶在多种应用场景中的表现远优于其多晶对应物。因此,生长大尺寸、高质量的单晶对于保证其最终器件性能具有重要意义。在此,基于我们最近发明的稳定温度和可控反溶剂扩散系统,本工作取得的改进包括以下几点:(1)我们对生长系统进行了改进,以优化对质量和热传输的控制,从而减少缺陷形成。生长出了具有最先进质量的MAPbBr晶体,并从块状晶体中制备出不同取向的晶体薄片,其X射线摇摆曲线的半高宽为40 - 86弧秒。(2)不同取向薄片的光学带隙没有显示出各向异性,而折射率和消光系数表现出明显的各向异性。(3)角分辨偏振拉曼光谱表明,(100)和(110)薄片上存在明显的面内各向异性,而(111)薄片上没有。推断平衡态MA取向采用<111>方向,相邻畴之间的MA取向反平行。(4)在不同取向薄片上制备的辐射探测器对可见光和X射线辐射均表现出光响应各向异性,一般顺序为(100)>(110)>(111)。由于各向异性是使用晶体材料的各种应用中不可避免的问题,本研究基于对伪立方晶格中有争议的固有偶极构型的阐明,将提供有关物理化学性质各向异性的定量信息,并随后有助于根据卤化物钙钛矿晶体的晶体取向优化器件性能。