A protocol detailing how shape-anisotropic colloidal cadmium chalcogenide nanocrystals can be covalently linked via their end facets is presented here.
Method Article
* These authors contributed equally
A protocol detailing how shape-anisotropic colloidal cadmium chalcogenide nanocrystals can be covalently linked via their end facets is presented here.
Here, we describe a protocol that allows for shape-anisotropic cadmium chalcogenide nanocrystals (NCs), such as nanorods (NRs) and tetrapods (TPs), to be covalently and site-specifically linked via their end facets, resulting in polymer-like linear or branched chains. The linking procedure begins with a cation-exchange process in which the end facets of the cadmium chalcogenide NCs are first converted to silver chalcogenide. This is followed by the selective removal of ligands at their surface. This results in cadmium chalcogenide NCs with highly reactive silver chalcogenide end facets that spontaneously fuse upon contact with each other, thereby establishing an interparticle facet-to-facet attachment. Through the judicious choice of precursor concentrations, an extensive network of linked NCs can be produced. Structural characterization of the linked NCs is carried out via low- and high-resolution transmission electron microscopy (TEM), as well as energy-dispersive X-ray spectroscopy, which confirm the presence of silver chalcogenide domains between chains of cadmium chalcogenide NCs.
The directed assembly of colloidal semiconductor NCs offers a synthetic pathway to the fabrication of nanostructures whose physicochemical properties are either the collective sum of or radically different from their individual NC building blocks1,2,3,4. Among the various approaches to nanoparticle assembly, the method of oriented attachment - in which NCs are essentially fused with each other - stands out as one that allows for interparticle electronic coupling. However, conventional oriented attachment typically requires the delicate balancing of particle dipole-, ligand- and solvent-based interactions that are generally difficult to execute and make applicable to different NC systems.
We have recently developed a wet-chemical method of covalently joining shape-anisotropic cadmium chalcogenide NCs by introducing a reactive inorganic intermediate through a site-selective nucleation process. The particles are subsequently linked by the spontaneous fusion of the reactive inorganic intermediate domains5. Although the technique is still based on an oriented attachment mechanism, there is much less need to consider weak interparticle interactions, thus allowing for more flexibility and control. The linking of shape-anisotropic cadmium chalcogenide NCs is carried out by first converting their tip facets to silver chalcogenide via a partial cation exchange process (in solution); this is followed by the selective removal of ligands passivating the surface. The NCs then come together via the fusion of the exposed silver chalcogenide facets, resulting in assemblies of cadmium chalcogenide NCs that are linked end-to-end.
In this protocol, we demonstrate that the linking technique can be applied to a variety of shape-anisotropic cadmium chalcogenide NCs (i.e., CdSe-seeded CdS NRs and CdSe-seeded CdSe NRs or TPs), yielding long linear NR chains or highly branched TP networks. These results suggest that the technique can be extended to a wide variety of NC shapes and metal chalcogenides amenable to silver cation exchange.
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1. Preparation of Precursor Stock Solutions
2. Synthesis of CdSe Quantum Dot (QD) Stock Solution
3. Synthesis of CdSe-seeded CdS NRs
Note: See8.
4. Synthesis of CdSe-seeded CdSe NRs
Note: See8.
5. Synthesis of CdSe-seeded CdSe TPs
Note: See10.
6. Facet Activation and the Linking of Nanostructures
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Using CdSe-seeded CdS NRs as a model system, as illustrated in Figure 1(a), we demonstrated that we can use a partial Ag+ exchange process to specifically transform the facets at the NR tips to Ag2S. The Ag2S facets are capped by DDA, which reacts with ODPA via an acid-base reaction to form an insoluble salt5. This causes the DDA ligands to be removed from the Ag2S facets, ca...
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The linking technique described in this work allows for shape-anisotropic cadmium chalcogenide nanoparticles that can undergo cation exchange with Ag+ to be joined, facet-to-facet, into assemblies such as linear chains or branched networks. Failure to form well-dispersed, extensive assemblies of facet-to-facet linked nanoparticles is often because of two reasons: (i) the ODPA is not dispersed well in the NR-containing solution, which can be addressed by sonicating the mixture for the prescribed amount of time ...
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We do not have anything to disclose.
This work was supported by JCO A*STAR Investigatorship grant (Project no. 1437C00135), A*STAR Science & Engineering Research Council Public Sector Funding (Project no. 1421200076), and a JSPS-NUS Joint Research Projects grant (WBS R143-000-611-133).
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| Name | Company | Catalog Number | Comments |
|---|---|---|---|
| Cadmium oxide (CdO), 99.5% | Sigma Aldrich | Highly toxic | |
| Tri-n-octylphosphine oxide (TOPO), 90 % and 99% | Sigma Aldrich | Technical and analytical grade | |
| Cadmium acetylacetonate (Cd(acac)2), 99.9% | Sigma Aldrich | Highly toxic | |
| Hexadecanediol (HDDO), 90% | Sigma Aldrich | Technical grade | |
| 1-octadecene (ODE), 90% | Sigma Aldrich | Technical grade | |
| Dodecylamine (DDA), 98% | Sigma Aldrich | Toxic | |
| Cadmium nitrate tetrahydrate ((CdNO3)2.4H2O), 98% | Sigma Aldrich | Highly toxic | |
| Myristic acid (MA), 99% | Sigma Aldrich | Analytical grade | |
| Octyl phosphonic acid (OPA), 97% | Sigma Aldrich | Analytical grade | |
| Oleylamine (Oly), 70% | Sigma Aldrich | Technical grade | |
| Hexadecyltrimethylammonium bromide (CTAB), 95% | Sigma Aldrich | Toxic | |
| Selenium pellets (Se, 5 mm), 99.99% | Sigma Aldrich | Analytical grade | |
| Hexadecylamine (HDA), 90% | Alfa Aesar | Technical grade, toxic | |
| n-tetradecylphosphonic acid (TDPA), 98% | Alfa Aesar | Analytical grade | |
| Silver nitrate (AgNO3), 99.9% | Alfa Aesar | Analytical grade | |
| Oleic acid (OA), 90% | Alfa Aesar | Technical grade | |
| Tri-n-octylphosphine (TOP), 97% | Strem | Analytical grade, toxic, air sensitive | |
| n-hexylphosphonic acid (HPA), 97% | Strem | Analytical grade | |
| n-octadecylphosphonic acid (ODPA), 97% | Strem | Analytical grade | |
| Tellurium powder (Te), 99.9% | Strem | Air sensitive | |
| Tri-n-butylphosphine (TBP), 99% | Strem | Analytical grade, highly toxic, air sensitive | |
| Diisooctylphosphonic acid (DIPA), 90% | Fluka | Technical grade, toxic |
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