Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots

被引:39
作者
Balan, Arunima D. [1 ,3 ,4 ]
Olshansky, Jacob H. [1 ,3 ,4 ]
Horowitz, Yonatan [1 ,3 ,4 ,5 ]
Han, Hui-Linp [1 ,3 ,4 ]
O'Brien, Erin A. [1 ,3 ,4 ]
Tang, Lucio [1 ]
Somorjai, Gabor A. [1 ,3 ,4 ]
Alivisatos, A. Paul [1 ,2 ,3 ,4 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Mat Sci & Engn, Berkeley, CA 94720 USA
[3] Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA
[4] Kavli Energy NanoSci Inst, Berkeley, CA 94720 USA
[5] Tel Aviv Univ, Sch Chem, Fac Exact Sci, IL-6997801 Tel Aviv, Israel
关键词
CdSe/CdS quantum dots; ligand phase transition; temperature-dependent photoluminescence; QD surface chemistry; interligand interactions; SELF-ASSEMBLED MONOLAYERS; SURFACE TRAPS; NANOCRYSTALS; TEMPERATURE; LUMINESCENCE; DYNAMICS; THERMODYNAMICS; FLUCTUATIONS; SIMULATION; NANORODS;
D O I
10.1021/acsnano.9b03054
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecyl-phosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell.
引用
收藏
页码:13784 / 13796
页数:13
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