Rainò Gabriele, Landuyt Annelies, Krieg Franziska, Bernasconi Caterina, Ochsenbein Stefan T, Dirin Dmitry N, Bodnarchuk Maryna I, Kovalenko Maksym V
Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences , ETH Zürich , CH-8093 Zürich , Switzerland.
Laboratory for Thin Films and Photovoltaics , Empa - Swiss Federal Laboratories for Materials Science and Technology , CH-8600 Dübendorf , Switzerland.
Nano Lett. 2019 Jun 12;19(6):3648-3653. doi: 10.1021/acs.nanolett.9b00689. Epub 2019 May 28.
Lead-halide perovskite APbX (A = Cs or organic cation; X = Cl, Br, I) nanocrystals (NCs) are the subject of intense research due to their exceptional characteristics as both classical and quantum light sources. Many challenges often faced with this material class concern the long-term optical stability, a serious intrinsic issue connected with the labile and polar crystal structure of APbX compounds. When conducting spectroscopy at a single particle level, due to the highly enhanced contaminants (e.g., water molecules, oxygen) over the NC ratio, deterioration of NC optical properties occurs within tens of seconds with typically used excitation power densities (1-100 W/cm) and in ambient conditions. Here, we demonstrate that choosing a suitable polymer matrix is of paramount importance for obtaining stable spectra from a single NC and for suppressing the dynamic photoluminescence blueshift. In particular, polystyrene (PS), the most hydrophobic among four tested polymers, leads to the best optical stability, one to two orders of magnitude higher than that obtained with poly(methyl methacrylate), a common polymeric encapsulant containing polar ester groups. Molecular mechanics simulations based on a force-field approximation corroborate the hypothesis that PS affords for a denser molecular packing at the NC surface. These findings underscore the often-neglected role of the sample preparation methodologies for the assessment of the optical properties of perovskite NCs at a single-particle level and guide the further design of robust single photon sources.
卤化铅钙钛矿APbX(A = Cs或有机阳离子;X = Cl、Br、I)纳米晶体(NCs)因其作为经典光源和量子光源的卓越特性而成为深入研究的对象。这类材料常常面临诸多挑战,其中长期光学稳定性问题备受关注,这是一个与APbX化合物不稳定且极性的晶体结构相关的严重内在问题。在单粒子水平进行光谱分析时,由于纳米晶体中污染物(如水分子、氧气)的比例大幅增加,在典型的激发功率密度(1 - 100 W/cm²)和环境条件下,纳米晶体的光学性质会在几十秒内发生劣化。在此,我们证明,选择合适的聚合物基质对于从单个纳米晶体获得稳定光谱以及抑制动态光致发光蓝移至关重要。特别是,聚苯乙烯(PS)在四种测试聚合物中疏水性最强,其光学稳定性最佳,比含有极性酯基的常见聚合物封装材料聚甲基丙烯酸甲酯(PMMA)高出一到两个数量级。基于力场近似的分子力学模拟证实了以下假设:聚苯乙烯在纳米晶体表面提供了更致密的分子堆积。这些发现强调了样品制备方法在单粒子水平评估钙钛矿纳米晶体光学性质时常常被忽视的作用,并为稳健的单光子源的进一步设计提供了指导。