Diorganyl dichalcogenides as useful synthons for colloidal semiconductor nanocrystals.

The ability to synthesize colloidal semiconductor nanocrystals in a well-controlled manner (i.e., with fine control over size, shape, size dispersion, and composition) has been mastered over the past 15 years. Much of this success stems from careful studies of precursor conversion and nanocrystal growth with respect to phosphine chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals. Despite the high level of success that has been achieved with phosphine chalcogenides, there has been a longstanding interest in exploring alternate chalcogenide precursors because of issues associated with phosphine chalcogenide cost, purity, toxicity, etc. This has resulted in a large body of literature on the use of sulfur and selenium dissolved in octadecene or amines, thio- and selenoureas, and silyl chalcogenides as alternate chalcogenide precursors for metal chalcogenide nanocrystal synthesis. In this Account, emerging work on the use of diorganyl dichalcogenides (R-E-E-R, where E = S, Se, or Te and R = alkyl, allyl, benzyl, or aryl) as alternate chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals is summarized. Among the benefits of these dichalcogenide synthons are the following: (i) they represent the first and only common precursor type that can function as chalcogen transfer reagents for each of the group VI elements (i.e., to make metal oxide, metal sulfide, metal selenide, and metal telluride nanocrystals); (ii) they possess relatively weak E-E bonds that can be readily cleaved under mild thermolytic or photolytic conditions; and (iii) the organic substituents can be tuned to affect the reactivity. These combined attributes have allowed dichalcogenide precursors to be employed for a wide range of metal chalcogenide nanocrystal syntheses, including those for In2S3, SnxGe1-xSe, SnTe, Cu2-xSySe1-y, ZnSe, CdS, CdSe, MoSe2, WSe2, BiSe, and CuFeS2. Interestingly, a number of metastable phases of compositionally complex semiconductors can be kinetically accessed through syntheses utilizing dichalcogenide precursors, likely as a result of their ability to convert at relatively low temperatures. These include the hexagonal wurtzite phases of CuInS2, CuInSe2, Cu2ZnSn(S1-xSex)4, and Cu2SnSe3 nanocrystals. The discovery of crystal phases on the nanoscale that do not exist in their bulk analogues is a developing area of nanocrystal chemistry, and dichalcogenides are proving to be a useful synthetic tool in this regard. The most recent application of dichalcogenide synthons for semiconductor nanocrystals is their use as precursors for surface ligands. While there is a rich history of using thiol ligands for semiconductor nanocrystals, the analogous selenol and tellurol ligands have not been studied, likely because of their oxidative instability. Dichalcogenides have proven useful in this regard, as they can be reduced in situ with diphenylphosphine to give the corresponding selenol or tellurol ligand that binds to the nanocrystal surface. This chemistry has been applied to the in situ synthesis and ligand binding of selenols to PbSe nanocrystals and both selenols and tellurols to CdSe nanocrystals. These initial studies have allowed the photophysics of these nanocrystal-ligand constructs to be investigated; in both cases, it appears that the selenol and tellurol ligands act as hole traps that quench the photoluminescence of the semiconductor nanocrystals.