Cl-capped CdSe nanocrystals via in situ generation of chloride anions.
Halide ions cap and stabilize colloidal semiconductor nanocrystal (NC) surfaces allowing for NCs surface interactions that may improve the performance of NC thin film devices such as photo-detectors and/or solar cells. Current ways to introduce halide anions as ligands on surfaces of NCs produced by the hot injection method are based on post-synthetic treatments. In this work we explore the possibility to introduce Cl in the NC ligand shell in situ during the NCs synthesis. With this aim, the effect of 1,2-dichloroethane (DCE) in the synthesis of CdSe rod-like NCs produced under different Cd/Se precursor molar ratios has been studied. We report a double role of DCE depending on the Cd/Se precursor molar ratio (either under excess of cadmium or selenium precursor). According to mass spectrometry (ESI-TOF) and nuclear magnetic resonance ((1)H NMR), under excess of Se precursor (Se dissolved in trioctylphosphine, TOP) conditions at 265 °C ethane-1,2-diylbis(trioctylphosphonium)dichloride is released as a product of the reaction between DCE and TOP. According to XPS studies chlorine gets incorporated into the CdSe ligand shell, promoting re-shaping of rod-like NCs into pyramidal ones. In contrast, under excess Cd precursor (CdO) conditions, DCE reacts with the Cd complex releasing chlorine-containing non-active species which do not trigger NCs re-shaping. The amount of chlorine incorporated into the ligand shell can thus be controlled by properly tuning the Cd/Se precursor molar ratio.
IMDEA Nanoscience, c\Faraday 9, Campus de Cantoblanco, 28049 Madrid, Spain. cristina.palencia.ramirez@chemie.uni-hamburg.de beatriz.hernandez@imdea.org.
Cristina
C
Palencia
Koen
K
Lauwaet
Leonor
L
de la Cueva
María
M
Acebrón
Julio J
JJ
Conde
Michaela
M
Meyns
Christian
C
Klinke
José M
JM
Gallego
Roberto
R
Otero
Beatriz H
BH
Juárez