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金-碲化镉纳米棒的超快动力学和单粒子光谱学。

Ultrafast dynamics and single particle spectroscopy of Au-CdSe nanorods.

机构信息

Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.

出版信息

Phys Chem Chem Phys. 2013 Feb 14;15(6):2141-52. doi: 10.1039/c2cp43458j. Epub 2013 Jan 4.

Abstract

Time-resolved photoluminescence (PL) and transient absorption (TA) spectroscopy are conducted in order to get knowledge on the excited state of CdSe nanorods (NR), and to assess the impact of Au nanoparticles (NP) on the carrier dynamics of hybrid Au-CdSe NRs. The decay dynamics measured in solution show an increase of non-radiative decay channels in the presence of Au NPs, whose characteristic lifetimes vary from a few ps to tens of ps. The ultrafast electron transfer from CdSe NRs to Au NPs efficiently competes with intraband relaxation dynamics, allowing observation of the hot-electron transfer process. Furthermore, the time-averaged PL decay of CdSe NRs shows a strongly multiexponential feature that was analyzed by single-particle spectroscopy. The PL decay of individual NRs fluctuates in time and is correlated with the PL intensity. We show that the time-averaged decay of bare CdSe NRs is composed of (i) a long lifetime component corresponding to bright CdSe NRs (ON state) and (ii) a short lifetime component corresponding to charged NRs that open additional fast non-radiative channels (OFF state). When Au NPs are attached to CdSe NRs, the ON state PL decays still show a long lifetime component, suggesting that the length of the NRs may hinder electron transfer if the exciton is formed far from the Au NPs. Finally, quantitative analysis of the OFF state decays shows that electron transfer occurs even in the presence of fast non-radiative pathways in charged systems.

摘要

为了了解 CdSe 纳米棒(NR)的激发态,并评估 Au 纳米粒子(NP)对混合 Au-CdSe NRs 载流子动力学的影响,进行了时间分辨光致发光(PL)和瞬态吸收(TA)光谱研究。在溶液中测量的衰减动力学表明,在 Au NPs 的存在下,非辐射衰减通道增加,其特征寿命从几个 ps 到几十个 ps 不等。从 CdSe NRs 到 Au NPs 的超快电子转移有效地与带内弛豫动力学竞争,从而允许观察到热电子转移过程。此外,CdSe NRs 的时间平均 PL 衰减呈现出强烈的多指数特征,这通过单粒子光谱进行了分析。单个 NR 的 PL 衰减随时间波动,并与 PL 强度相关。我们表明,裸 CdSe NRs 的时间平均衰减由(i)对应于亮 CdSe NRs 的长寿命分量(ON 状态)和(ii)对应于打开附加快速非辐射通道的带电 NRs 的短寿命分量组成(OFF 状态)。当 Au NPs 附着在 CdSe NRs 上时,ON 状态的 PL 衰减仍然显示出长寿命分量,这表明如果激子远离 Au NPs 形成,NRs 的长度可能会阻碍电子转移。最后,对 OFF 状态衰减的定量分析表明,即使在带电体系中存在快速非辐射途径,电子转移也会发生。

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