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中国物理学会期刊

混合型碘系钙钛矿薄膜变温光致发光特性的研究

Temperature-dependent photoluminescence in hybrid iodine-based perovskites film

CSTR: 32037.14.aps.68.20191238
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  • 研究了阴离子和阳离子混合型碘系钙钛矿薄膜材料的结构、光学性质及光致发光温度特性. 研究发现, 阴离子混合型碘系钙钛矿(MAPb(BrxI1–x)3, MA+ = \rmC\rmH_\rm3\rmNH_3^ + )随着半径较小的Br离子的比例增加(x = 0—0.1), 薄膜择优取向生长更明显, 其光学带隙从1.43 eV到1.48 eV线性增加. 在光抽运下, 随着工作温度从10 K升高到125 K, 纯碘系钙钛矿(MAPbI3, 即x = 0)可见区光致发光(PL)的峰位轻微的红移; 之后至350 K, 发生蓝移. 而Br阴离子混合型钙钛矿薄膜的PL峰位只随温度升高持续蓝移. 并且在不同工作温度下, Br阴离子比例x与PL峰位呈现线性关系. 对于纯碘系钙钛矿, 其高温段激子结合能是37.5 meV; 随着Br的比例的增加, 高温段激子结合能会先增大后减小. 当x = 0.0333, 其薄膜PL半高宽随温度升高展宽幅度最小, 具有更好的温度稳定性. 通过进一步三重阳离子混合和阴离子调节, 获得更加优良的混合型碘系钙钛矿((Cs0.05(FA0.85MA0.15)0.95)Pb(Br0.15I0.85)3, FA+ = \rmHC(\rmN\rmH_2)_2^ +)薄膜, 为进一步研制太阳能电池和发光器件奠定了实验基础.

     

    Lead halide perovskite has attracted much attention due to its high absorption coefficient, long carrier diffusion length, low binding energy, and low cost. The stability of intrinsic crystal structure in I-based perovskite can be theoretically estimated by calculating cubic structures factor and octahedral factor. Experimental methods to solve the stability of structure in I-based perovskite could be mainly to either incorporate anions (e.g. Cl, Br) or mix cations (e.g. Cs+) into I-based perovskite matrix. Moreover, incorporating Br into I-based perovskite leads its band gap to widen, which might be used as a top-cell material to tandem solar cell. However, in order to understand photo-physics process of anion-mixed and/or cation-mixed perovskites, it is essential to further investigate the optical properties such as absorption spectrum, photoluminescence (PL), temperature-dependent PL (TPL) behavior, etc. In this work, anion-mixed and/or cation-mixed perovskite thin films with high quality crystallization and (110) prereferral orientation are synthesized by one-step solution method. All mixed perovskite films are characterized by using X-ray diffraction (Rigaku D MAX-3C, Cu-Kα, λ = 1.54050 Å) and X-ray photoelectron spectroscopy (XPS) (Thermo Scientific Escalab 250Xi). A set of strong peaks of the mixed perovskite films at 14.12° and 28.48°, is assigned to (110) and (220) lattice plane of orthorhombic crystal structure of I-based perovskite, due to preferred orientation. The Pb 4f and I 3d doublet peaks, corresponding to Pb+2 and I states, are observed in XPS spectra. It should be noted that in the absence of other valence states of Pb and I component at lower/upper binding energy, the chemical element composition ratio of Pb+2 and I are close to stoichiometric proportion. For optical absorptionspectra, the optical bandgaps of the perovskite films increase with doping concentration of Br increasing. For TPL, the perovskite films with x = 0 and x = 0.05 show abnormal red-shifts in a temperature range from 10 to 100 K. The following blue shifts in a temperature range from 125 to 350 K emerge, which is mainly attributed to band gap widening. However, incorporating more Br into I-based perovskite leads the TPL spectra to monotonically blue-shift. A linear relationship between the TPL peak position and the doping concentration of Br ions is observed at the same temperatures. This indicates that the Br anion in I-based perovskite plays a crucial role in determining the optical properties. The low-temperature and high-temperature (HT) excitonic binding energy at x = 0 are 186 meV and 37.5 meV, respectively. The HT excitonic binding energy first increases and then decreases with the Br concentration in I-based perovskite film increasing. The minimal variation of TPL peak position and FWHM (full width at half maximum) at x = 0.0333 are 13 nm and (25.8 ± 0.5) meV, respectively, suggesting higher temperature stability in optical property. This should contribute to understanding the relationship between temperature-dependent electrical and optoelectronic performance for hybrid mixed perovskite materials and devices.

     

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