Semiconductor nanocrystal high-temperature synthesis

The reactions used for synthesis of II-VI (CdSe, CdTe), III-V (InP, InAs), and IV-VI (PbS, PbSe, PbTe) semiconductor nanocrystals are outlined by Schemes 3-5.4,17,30-32 The syntheses are carried out at high temperatures, and in the presence of long-chain alkylphosphines (trioctylphosphine,TOP), alkyl-phosphine oxides (trioctylphosphine oxide, TOPO), alkylamines (hexadecyl-amine, HD A), and alkylphosphonic acids as the stabilizing agents. 

The hot-soup method has also been applied to the production of semiconductor core/shell nanostructures, where a semiconductor nanocrystal is coated with a second semiconductor of wider bandgap. Shown in Figure 23 is a scheme for the synthesis of CdSe/CdS core/shell nanocrystals. These nanostructures were synthesized via a high-temperature route in a mixture of TOP and TOPO (223,224) and via a low-temperature route in pyridine (225). Among the semiconductor core/shell nanomaterials produced were CdSe/ZnS, CdSe/CdS, InAs/InP, InAs/CdSe, InAs/ZnSe, and InAs/ZnS (223,225-228). In these structures, the shell type and thickness allow further control of the optical, electronic, and other properties of semiconductor nanocrystals. For example, the shell may be used to passivate the imperfect surface of the core semiconductor, resulting in significantly improved luminescence efficiency. 

In 2002, Rosenthal and co-workers reported using semiconductor nanocrystals as visual aides for introducing the particle-in-a-box concept to juniors and seniors in physical chemistry (P). However, at that time, the best chemical procedure for producing large quantities of high quahty quantum dots was based on the work of Murray 10, 11). In this method, dimethyl cadmium, an extremely toxic and pyrophoric substance, was reacted at high temperatures under an inert atmosphere. The synthesis was expensive, difficult to control, and could potentially become explosive, certainly not a method suitable for an introductory laboratory with novice laboratoiy students. 

Historically, QDs were first synthesized in glass matrices where the slow difiusion of precursors provided some measure of size control. In the last couple of decades, colloidal techniques have advanced to the point that parameters such as precursor reactivity, temperature, surfactants etc. can be independently tuned to control and regulate nanocrystal formation. This enables the synthesis of high quality solvent dispersible particles that may be further processed using simple wet-chemical methods. Qne of the earliest techniques employed to achieve this is known as the arrested precipitation method where the semiconductor growth is arrested after the... 

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