以化學氣相沉積合成生長錳摻雜鈣鈦礦奈米粒子及其於中孔洞沸石中之限制生長

Abstract

本研究以高表面積（SBET > 800 m2 / g）的中孔沸石奈米粒子（mesoporous zeolite nanoparticles, MZNs）做為基材，於高溫下（700-900°C）溴化鉛與溴化銫為前驅物進行化學氣相沉積（chemical vapor deposition, CVD）反應，合成中孔洞限制的CsPbBr3/Cs4PrBr6的鈣鈦礦（pervoskite）奈米粒子。鈣鈦礦奈米粒子大小可以藉由前驅物比例及溫度改變加以調控，其電子結構及型貌利用紫外-可見光譜儀、螢光光譜儀、X-光繞射及穿透式電子顯微鏡佐證。合成過程中引入鎂離子及具有未成對電子的錳離子，使摻雜之鈣鈦礦奈米粒子放光具有不同波長，其結構組成、電子結構及自旋特性，以感應偶合電漿質譜、X光繞射光譜、螢光光譜及電子順磁共振光譜儀證實。此外，使用具半導體特性的中孔氧化石墨烯奈米粒子（mesoporous graphene-oxide nanoparticles, MGNs）做為基材時，可有效增進電荷分離效率，於照光下可使二氧化碳還原成一氧化碳，並以紫外-可見光譜儀及螢光光譜佐證其電子結構之變化。無機鈣鈦礦材料具良好的發光及催化效能，未來欲結合中孔洞薄膜材料之生長，生長具大氣穩定之太陽能轉換材料，提供異質結構於中孔洞沸石材料上限制生長之研究。

In this study, mesoporous zeolite nanoparticles (MZNs) with high surface area (SBET>800 m2/g) was used as robust substrates to synthesize spatially confined CsPbBr3/Cs4PrBr6 (perovskite) nanoparticles (PV@MZNs) via chemical vapor deposition (CVD) at high temperature (700-900 °C) with two precursors, CsBr and PbBr2. The grain sizes of the perovskites were modulated by precursor ratios and reaction temperature. Ultraviolet-visible absorption spectroscopy (UV-Vis), fluorescence spectroscopy (FS), X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) were utilized to characterize electronic structures and crystals of PV@MZNs. Magnesium and manganese ions were introduced to dope the perovskites, showing unique phosphorescence property. The characterizations of compositions, electronic and spin structures were assured by induced coupled plasma mass spectrometry, XRD, FS and electron paramagnetic resonance, individually. Moreover, heterostructures for PV@MZNs can be created when mesoporous graphene-oxide nanoparticles (MGNs) were introduced. Charge separation can be observed by fluorescence quenching and photocatalytic CO2 reductions into CO. Inorganic perovskite materials with excellent optical and catalytic performance, combined with mesoporous zeolite thin films (MZTFs) and heterostructures showing confined dimensions on silicon substrates, are rationally targeted for stable ambient solar energy converters.