Exploiting Cation Exchange Reactions in Doped Colloidal NIR Semiconductor Nanocrystals: from synthesis to applications

Colloidal quantum dots (CQDs) have tunable optical properties through manipulation of their size, shape, and surface chemistry. Among pholuminescent QDs, near-infrared (NIR) emitting ones are of particular interest since they can be used in several applications, from the labeling in living tissues, to the integration in commercial optoelectronic devices, like photovoltaics for solar energy conversion or photodetectors from visible to the near-infrared and mid-infrared. In addition, the exciting promise of CQDs is that is associated with easy and low-cost device fabrication process. In fact, solution-based techniques like spin-coating, dip coating and ink-jet printing are typically used for solution CQDs readily to be used in large-area processing techniques. Thus, to obtain an ink solution of nanocrystals (NCs) ready to be used in device fabrication process, in this thesis, cation exchange (CE) reactions have been used as a convenient tool to finely transform NCs directly in solution or deposited as thin films. These reactions allow to substitute a fraction or all “host” metal cations of pre-synthesized NCs with new “guest” cations while preserving both NCs’ size, shape and, typically, crystal structure. Depending on the miscibility of the reactant and product materials, and on the kinetics of the CE reaction, different types of nanostructures can be accessed ranging from alloy NCs, doped systems, dimers, core@shell (or core@graded-shell) heterostructures even with elaborated architectures (i.e., quantum wells, multiple-cores@shell). Unlike ion substitution in solids, cation exchange at nanoscale results in fast reaction rate and an easy modulation of the thermodynamics through selective ion coordination in solution. This study provides an overview of the CE on semiconductor NCs, in particular on II-VI, I-III-VI2 and III-VI compounds. We first explore the exchange between cadmium chalcogenides and mercury ions to produce Cd1-xHgxTe CQDs which can be potentially employed in NIR photodetectors and photovoltaic devices. Our developed synthesis is a result of a wide systematic investigation process, in which we varied specific physical parameters, such as the reaction temperature, the feed molar ratio of the precursor and the solvent. More specifically, these aspects were studied to have control on the size, shape, surface composition and crystalline phase after mild conditions of annealing into stable connected crystals. This peculiarity could be exploited to boost the photogenerated charges diffusion in polycrystalline photoconducting films fabricated by means of an ink of NCs solution. Additionally, another aspect studied was the surface passivation of Cd1-xHgxTe colloidal NCs, in order to understand how to optimize the charge transfer efficiency among the nanocrystals. The carrier transport in QD devices differs fundamentally from band transport in bulk semiconductors. In nanocrystal film it is of fundamental relevance to improve the mobility of the photogenerated charges. Noteworthy, the granularity of the system and the consequent coupling between adjacent dots can produce additional physical parameters, as charge recombination. The carrier diffusion length can be limited by trapping sites1. To overcome these limitations, post-synthetic strategies that couple the high quality NCs solutions with ideal properties (band gap, absorption, monodispersivity) and high-quality films (quantum dot packing, passivation, and absorptive/conductive properties) are necessary. Indeed, to improve the inter-NCs conductivity in a NC film, ligand exchange and stripping procedures are widely used, with the aim of replacing insulating surfactants with more conductive species. These procedures have some drawbacks, for example metal cations can desorb from the surface of the NCs during the stripping. On the contrary, here we will show how our nano heterostructures (NHCs) enable to avoid the post-process ligand stripping and to perform the final annealing step in milder conditions. Above these considerations, CE can be exploited to address NCs solution through surface uniformity from the nano- to the macroscopic scale. This is the first step toward electronic coupling between the separate building blocks of nanocrystals. Apart from III-V QDs, we shifted our research activity on valid alternative material which do not contain toxic heavy metals such as Cd, Pb, As or Hg, and that offer a high flexibility for tuning band gap in the NIR window. In chapter 5, the results about the study of a III-V system are reported. Thus, we studied InP system, which is probably the only one that could provide a compatible emission color range similar to that of Cd-based QDs but without intrinsic toxicity. Nevertheless, the synthesis of III-V NCs, due to their covalent-bond character, is limited by long reaction times or an uncontrollably fast nucleation that may lead to the formation of amorphous or bulk compounds. The role of our work is to explore the reported InP synthesis and to further improve the luminescent properties of these systems Here we study the effect of different parameter (molar concentration in reaction mixture, the use of different phosphorous precursors) to enhance the control over the particle size and size distribution. After that, we studied different Sulphur source precursors to obtain InP@ZnS core@shell NCs with high quantum Yield (QY). In the last chapter, we describe also I-III-VI2 system as CuInS2 for photoluminescence modulation. In this Chapter Copper Indium Sulfide nanocrystals are prepared using a single-step heating up method relying on the low thermal stability of ter- dodecanethiol used as stabilizing agent, solvent, and sulfur precursors. The obtained particles exhibit an emission varying from 710 to 940 nm. This range depends on the extent of the heating time (pre-heating) before the threshold temperature of 230°C for the growth process of ternary semiconductor NCs such as of CIS nanocrystals. Afterwards we report on the procedure for the growth of a ZnS shell, which enables a blueshift of the PL emission wavelength with respect to those of their parent CIS, due to the widening of the band gap for the entrance of zinc ions into the CIS structures.