Energy levels in the band gap arising from surface states can dominate the optical and electronic properties of semiconductor nanocrystal quantum dots (QDs). Recent theoretical work has predicted that such trap states in II–VI and III–V QDs arise only from two-coordinated anions on the QD surface, offering the hypothesis that Lewis acid (Z-type) ligands should be able to completely passivate these anionic trap states. In this work, we provide experimental support for this hypothesis by demonstrating that Z-type ligation is the primary cause of PL QY increase when passivating undercoordinated CdTe QDs with various metal salts. Optimized treatments with InCl3 or CdCl2 afford a near-unity (>90%) photoluminescence quantum yield (PL QY), whereas other metal halogen or carboxylate salts provide a smaller increase in PL QY as a result of weaker binding or steric repulsion. The addition of non-Lewis acidic ligands (amines, alkylammonium chlorides) systematically gives a much smaller but non-negligible increase in the PL QY. We discuss possible reasons for this result, which points toward a more complex and dynamic QD surface. Finally we show that Z-type metal halide ligand treatments also lead to a strong increase in the PL QY of CdSe, CdS, and InP QDs and can increase the efficiency of sintered CdTe solar cells. These results show that surface anions are the dominant source of trap states in II–VI and III–V QDs and that passivation with Lewis acidic Z-type ligands is a general strategy to fix those traps. Our work also provides a method to tune the PL QY of QD samples from nearly zero up to near-unity values, without the need to grow epitaxial shells.
The efficiency of nanocrystal (NC)-based devices is often limited by the presence of surface states that lead to localized energy levels in the bandgap. Yet, a complete understanding of the nature of these traps remains challenging. Although theoretical modeling has greatly improved our comprehension of the NC surface, several experimental studies suggest the existence of metal-based traps that have not yet been found with theoretical methods. Since there are indications that these metal-based traps form in the presence of excess electrons, the present work uses density functional theory (DFT) calculations to study the effects of charging II–VI semiconductor NCs with either full or imperfect surface passivation. It is found that charge injection can lead to trap-formation via two pathways: metal atom ejection from perfectly passivated NCs or metal–metal dimer-formation in imperfectly passivated NCs. Fully passivated CdTe NCs are observed to be stable up to a charge of two electrons. Further reduction leads to charge localization on a surface Cd atom and the formation of in-gap states. The effects of suboptimal passivation are probed by charging NCs where an X-type ligand is removed from the (100) plane. In this case, injection of even one electron leads to Cd-dimerization and trap-formation. Addition of an L-type amine ligand prevents this dimer-formation and is suggested to also prevent trapping of photoexcited electrons in charge neutral NCs. The results presented in this work are generalized to NCs of different sizes and other II–VI semiconductors. This has clear implications for n-doping II–VI semiconductor NCs without introducing surface traps due to metal ion reduction. The possible effect of these metal ion localized traps on the photoluminescence efficiency of neutral NCs is also discussed.
Van der Waals heterostructures consisting of graphene and transition metal dichalcogenides have shown great promise for optoelectronic applications. However, an in-depth understanding of the critical processes for device operation, namely, interfacial charge transfer (CT) and recombination, has so far remained elusive. Here, we investigate these processes in graphene-WS2 heterostructures by complementarily probing the ultrafast terahertz photoconductivity in graphene and the transient absorption dynamics in WS2 following photoexcitation. We observe that separated charges in the heterostructure following CT live extremely long: beyond 1 ns, in contrast to ~1 ps charge separation reported in previous studies. This leads to efficient photogating of graphene. Furthermore, for the CT process across graphene-WS2 interfaces, we find that it occurs via photo-thermionic emission for sub-A-exciton excitations and direct hole transfer from WS2 to the valence band of graphene for above-A-exciton excitations. These findings provide insights to further optimize the performance of optoelectronic devices, in particular photodetection.
In transient absorption (TA) measurements on Cd-chalcogenide quantum dots (QDs), the presence of a band-edge (BE) bleach signal is commonly attributed entirely to conduction-band electrons in the 1S(e) state, neglecting contributions from BE holes. While this has been the accepted view for more than 20 years, and has often been used to distinguish electron and hole kinetics, the reason for the absence of a hole contribution to the BE-bleach has remained unclear. Here, we show with three independent experiments that holes do in fact have a significant impact on the BE-bleach of well-passivated Cd-chalcogenide QD samples. Transient absorption experiments on high photoluminescence quantum yield CdSe/CdS/ZnS core–shell–shell QDs clearly show an increase of the band-edge bleach as holes cool down to the band edge. The relative contribution of electron-to-hole bleach is 2:1, as predicted by theory. The same measurements on core-only CdSe QDs with a lower quantum yield do not show a contribution of holes to the band-edge bleach. We assign the lack of hole bleach to the presence of ultrafast hole trapping in samples with insufficient passivation of the QD surface. In addition, we show measurements of optical gain in core–shell–shell QD solutions, providing clear evidence of a significant hole contribution to the BE transient absorption signal. Finally, we present spectroelectrochemical measurements on CdTe QDs films, showing the presence of a BE-bleach for both electron and hole injections. The presence of a contribution of holes to the bleach in passivated Cd-chalcogenides QDs bears important implications for quantitative studies on optical gain as well as for TA determinations of carrier dynamics.
Indium phosphide quantum dots are the main alternative for toxic and restricted Cd-based quantum dots for lighting and display applications, but in the absence of protecting ZnSe and/or ZnS shells, InP quantum dots suffer from low photoluminescence quantum yields. Traditionally, HF treatments have been used to improve the quantum yield of InP to ∼50%, but these treatments are dangerous and not well understood. Here, we develop a postsynthetic treatment that forms HF in situ from benzoyl fluoride, which can be used to strongly increase the quantum yield of InP core-only quantum dots. This treatment is water-free and can be performed safely. Simultaneous addition of the z-type ligand ZnCl 2 increases the photoluminescence quantum yield up to 85%. Structural analysis via XPS as well as solid state and solution NMR measurements shows that the in situ generated HF leads to a surface passivation by indium fluoride z-type ligands and removes polyphosphates, but not PO 3 and PO 4 species from the InP surface. With DFT calculations it is shown that InP QDs can be trap-free even when PO 3 and PO 4 species are present on the surface. These results show that both polyphosphate removal and z-type passivation are necessary to obtain high quantum yields in InP coreonly quantum dots. They further show that core-only InP QDs can achieve photoluminescence quantum yields rivalling those of InP/ZnSe/ZnS core/shell/shell QDs and the best core-only II−VI QDs.
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