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Morphology Control of Cadmium Selenide Nanocrystals: Insights into the Roles of Di-n-octylphosphine Oxide (DOPO) and Di-n-octylphosphinic Acid (DOPA)

机译:硒化镉纳米晶体的形态控制:洞察的角色二 - 正辛基氧化膦(DOpO)和二 - 正octylphosphinic酸(DOpa)

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摘要

Di-n-octylphosphine oxide (DOPO) and di-n-octylphosphinic acid (DOPA), as two of impurities found in commercial tri-n-octylphosphine oxide (TOPO), generate significant differences in the outcomes of CdSe-nanocrystal (NC) syntheses. Using n-tetradecylphosphonic acid (TDPA) as the primary acid additive, quantum dots (QDs) are grown with DOPO added, whereas quantum rods (QRs) are grown in the presence of DOPA. While using oleic acid (OA) as the primary acid additive, QDs are generated and the QDs produced with DOPA exhibit larger sizes and size distributions than those produced with DOPO. 31P NMR analyses of the reaction mixtures reveal that the majority of the DOPO has been converted into DOPA and di-n-octylphosphine (DOP) with DOP being removed via evacuation over the course of Cd-precursor preparation. The origin of the puzzling differences in the shape control of CdSe NCs in the presence of DOPO and DOPA is elucidated to be the small quantity of DOPO present, which liberates DOP during NC synthesis. In the presence of DOP, regardless of DOPA, the precursor-conversion kinetics and thus the nucleation kinetics are dramatically accelerated, generating a large number of nuclei by consuming a significant amount of CdSe nutrients, favoring QD growth. Similarly, QD growth is favored by the fast nucleation kinetics in the presence of OA, and the broader size distributions of QDs with DOPA are due to a second nucleation event initiated by the more stable Cd-di-n-octylphosphinate component. In contrast, a slow nucleation event results in the growth of QRs in the case of using DOPA and TDPA, where no DOPO or DOP is present. The results thus demonstrate the important role of precursor-conversion kinetics in the control of NC morphologies.
机译:Di-N-辛膦酰氧化物(DOPO)和二 - 正辛基次膦酸(DOPA),如商业三 - 辛基膦(TOPO)中发现的两种杂质,在CDSE纳米晶体(NC)的结果中产生显着差异合成。使用N-十四烯基膦酸(TDPA)作为初级酸添加剂,用DOPO加入量子点(QDS),而量子棒(QRS)在DOPA存在下生长。在使用油酸(OA)作为初级酸添加剂时,产生QD的QD,并且DOPA产生的QD具有比用DOPO生产的尺寸和尺寸分布的QD。 31 / sup> P反应混合物的P nMR分析表明,大部分DOPO已经转化为DOPA和DI-N-辛基膦(DOP),通过在CD-前体制备过程中通过抽空除去DOP 。在DOPO和DOPA存在下CDSE NCS形状控制的令人难题差异的起源被阐明为存在的少量存在的DOPO,其在NC合成期间释放DOP。在存在DOP的情况下,无论多巴,前体转化动力学和核酸动力学都是显着加速的,通过消耗大量的CDSE营养物产生大量核来产生大量的核心,有利于QD生长。类似地,QD生长受到在oA存在下的快速成核动力学的青睐,并且具有多巴的Qds的较宽尺寸分布是由于由更稳定的Cd-Di-Z-辛基膦酸膦组分引发的第二核事件。相反,在使用DOPA和TDPA的情况下,慢核事件导致QRS的生长,其中没有任何多孔或DOP。因此,结果证明前体转化动力学在NC形态控制中的重要作用。

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  • 作者

    Fudong Wang; William E. Buhro;

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  • 年(卷),期 -1(134),11
  • 年度 -1
  • 页码 5369–5380
  • 总页数 28
  • 原文格式 PDF
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