We review the synthesis of semiconductor nanocrystals/colloidal quantum dots in organic solvents with special emphasis on earth-abundant and toxic heavy metal free compounds. Following the Introduction, section 2 defines the terms related to the toxicity of nanocrystals and gives a comprehensive overview on toxicity studies concerning all types of quantum dots. Section 3 aims at providing the reader with the basic concepts of nanocrystal synthesis. It starts with the concepts currently used to describe the nucleation and growth of monodisperse particles and next takes a closer look at the chemistry of the inorganic core and its interactions with surface ligands. Section 4 reviews in more detail the synthesis of different families of semiconductor nanocrystals, namely elemental group IV compounds (carbon nanodots, Si, Ge), III–V compounds (e.g., InP, InAs), and binary and multinary metal chalcogenides. Finally, the authors’ view on the perspectives in this field is given.

Synthesis of Semiconductor Nanocrystals, Focusing on Nontoxic and Earth-Abundant Materials.

Quantum-sized ZnS nanocrystals with quasi-spherical and rod shapes were synthesized by the aging reaction mixtures containing diethylzinc, sulfur, and amine. Uniform-sized ZnS nanorods with the average dimension of 5 nm × 21 nm, along with a small fraction of 5 nm-sized quasi-spherical nanocrystals, were synthesized by adding diethylzinc to a solution containing sulfur and hexadecylamine at 125 °C, followed by aging at 300 °C. Subsequent secondary aging of the nanocrystals in oleylamine at 60 °C for 24 h produced nearly pure nanorods. Structural characterizations showed that these nanorods had a cubic zinc blende structure, whereas the fabrication of nanorods with this structure has been known to be difficult to achieve via colloidal chemical synthetic routes. High-resolution TEM images and reaction studies demonstrated that these nanorods are formed from the oriented attachment of quasi-spherical nanocrystals. Monodisperse 5 nm-sized quasi-spherical ZnS nanocrystals were separately synthesized by adding ...

Synthesis of quantum-sized cubic ZnS nanorods by the oriented attachment mechanism.

The successful transition of any nanocrystal-based product from the research phase to the commercial arena hinges on the ability to produce the required nanomaterial on large scales. The synthesis of colloidal nanocrystals using a heat-up (non-injection) method is a reliable means to achieve high quality nanomaterials on large scales with little or no batch-to-batch variation. In this class of synthesis precursors are heated within a reaction medium to induce a chemical reaction that yields monomer for nucleation and growth. Use of the heat-up technique circumvents the pitfalls of mixing time and poor heat management inherent to classical “hot-injection” methods. In heat-up syntheses monomer is produced in a more continuous fashion during the heating stage, making it more difficult to separate the nucleation and growth stages of the reaction, a factor that is conventionally considered detrimental toward achieving homogeneous colloidal dispersions. However, through the judicious selection of precursors, st...

The heat-up synthesis of colloidal nanocrystals

Precursor Chemistry for Main Group Elements in Semiconducting Materials

We report a low-temperature (150 °C) and simple synthesis of quasi-monodispersed and uniform hexagonal (Wurtzite) ZnS nanocrystals in ethylene glycol medium. The samples structures were characterized with X-ray diffraction technique and transmission electron microscopy. It is believed that ethylene glycol medium plays a key role in forming hexagonal ZnS which is a stable phase at high temperatures.

Low-Temperature Synthesis of Hexagonal (Wurtzite) ZnS Nanocrystals

A synthesis of various metal sulfide nanoparticles at relatively low temperature with use of a single precursor under ambient conditions is described. Metal alkyl xanthates (as well as thiocarbamates and thiocarbonates) are used as the precursor. Lewis base alkylamine solvents promote the reaction at low temperatures (from below room temperature up to ∼150 °C). By this method we form crystalline particles which are size- and shape-tunable and are usually monodiserse. This tunability is achieved by controlling parameters such as the reaction temperature, the reaction time, the concentration of the precursor, and the alkyl chain length. Core/shell structures are synthesized with the same method, using the same precursors, applying either a single-step or a dual-step process. CdS spherical particles, for instance, exhibit a narrow (∼30 nm fwhm) tunable excitonic fluorescence, and a broad, long wavelength defect emission, which intensity can be adjusted in a controlled manner, and even totally eliminated. Qua...

and Beni Katz

Papers

Synthesis of high-quality metal sulfide nanoparticles from alkyl xanthate single precursors in alkylamine solvents