Environmentally friendly nanocrystals (NCs) such as InP are in demand for various applications, such as biomedical labeling, solar cells, sensors, and light-emitting diodes (LEDs). To fulfill their potential applications, the synthesis of such high-quality "green" InP NCs required further improvement so as to achieve better stability, higher brightness NCs, and also to have a more robust synthesis route. The present study addresses our efforts on the synthesis of high-quality In(Zn)P/ZnS core-shell NCs using an air- and moisture-stable ZnS single molecular precursor (SMP) and In(Zn)P cores. The SMP method has recently emerged as a promising route for the surface overcoating of NCs due to its simplicity, high reproducibility, low reaction temperature, and flexibility in controlling the reaction. The synthesis involved heating the In(Zn)P core solution and Zn(S2CNR2) (where R = methyl, ethyl, butyl, or benzyl and referred to as ZDMT, ZDET, ZDBT, or ZDBzT, respectively) in oleylamine (OLA) to 90-250 °C for 0.5-2.5 h. In this work, we systematically studied the influence of different SMP end groups, the complex formation and stability between the SMP and oleylamine (OLA), the reaction temperature, and the amount of SMP on the synthesis of high-quality In(Zn)P/ZnS NCs. We found that thiocarbamate end groups are an important factor contributing to the low-temperature growth of high-quality In(Zn)P/ZnS NCs, as the end groups affect the polarity of the molecules and result in a different steric arrangement. We found that use of SMP with bulky end groups (ZDBzT) results in nanocrystals with higher photoluminescence quantum yield (PL QY) and better dispersibility than those synthesized with SMPs with the shorter alkyl chain groups (ZDMT, ZDET, or ZDBT). At the optimal conditions, the PL QY of red emission In(Zn)P/ZnS NCs is 55 ± 4%, which is one of the highest values reported. On the basis of structural (XAS, XPS, XRD, TEM) and optical characterization, we propose a mechanism for the growth of a ZnS shell on an In(Zn)P core.

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For hybrid solar cells, interfacial chemistry is one of the most critical factors for good device performance. We have demonstrated that the size of the surface ligands and the dispersion of nanoparticles in the solvent and in the polymer are important criteria in obtaining optimized device performance. The size of the ligands will affect the charge transport at the particle/particle and particle/polymer interfaces and the chemical structures of the ligands will determine their compatibility with the solvent and polymer. Hence other than pyridine, 2-thiophenemethylamine also showed good potential as ligand replacement for poly(3-hexylthiophene)/CdSe hybrid solar cells. With the right ligand combination, we have shown that the power conversion efficiency improved by a factor of 6 after ligand exchange.

New 3D supramolecular networks S1 and S2 were prepared by Zn(II) coordination of the tetraphenylmethane-based p-type and n-type molecules bearing four terpyridine ligands. XRD and BET results indicate they are relatively amorphous and non-porous with a high degree of interpenetration within the networks. These could be disassembled by adding more Zn(II) ions and reassembled to form extended 3D networks S3-6 by inserting linear n-type or p-type linking units. BET data suggests that these expanded networks are more porous than the original networks S1-2, but the low porosity and surface area suggest a high degree of interpenetration remains within the expanded networks. The optical properties of these materials were compared to the linear polymers P1-3 made by Zn(II)-mediated assembly of the same linear linking units. The emission spectra of both the 3-D and 1-D cases with the same linking unit matched each other, confirming the incorporation of the linker units into the expanded assemblies. This shows that metal-ligand mediated self-assembly can be used to make two component systems in which the optical properties can be tuned by selection of the units. The assembly was also performed in the presence of CdSe nanocrystals to form nanocomposites.

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