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an array of nanocrystals separated by energy barriers (a so-called nanocrystal solid ) depends on matching the energy levels of neighboring nanocrystals (site energies, ), on the exchange coupling energy between the nanocrystals ( ), and on the Coulomb charging energy of the nanocrystal array (Ec)71 73 In an ensemble of strongly con ned semiconductor nanocrystals, is mostly determined by particle size dispersion The strength of exchange coupling depends on interparticle spacing , the chemical nature of nanocrystals, capping ligands, and in some cases, on the relative orientation of the nanocrystals scales approximately as exp( (d + )), where d is the nanocrystal diameter and 1 describes the length scale of the wavefunction leakage outside the nanocrystal71,72 The charging energy Ec of a spherical nanocrystal of diameter d can be estimated as EC = e2/(4 m 0d), where m is the dielectric constant of the surrounding medium.



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For ef cient charge transport, the dispersion of site energies should not exceed or Anderson localization will dominate the transport properties If < Ec, the nanocrystal array can behave as a Mott insulator71 Numerous early studies revealed low electronic conductivity in semiconductor nanocrystal arrays because of poor exchange coupling and large concentrations of dangling bonds at the nanocrystal surfaces, which introduce carrier trapping mid-gap states69,74,75 The electron mobility can be increased by electrochemically charging the nanocrystal solid with several additional electrons per nanocrystal70,74 Charge screening by mobile ions present in the electrolyte substantially reduces Ec, facilitating the charging of a nanocrystal solid71 The mobility increases because of a combination of trap lling and transport through multiple quantum con ned electronic states (eg, 1S, 1P).





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70 However, real technological implementations require solid-state eld-effect transistors with insulated gates, where the current is modulated by applying a potential to a gate capacitively coupled to the transistor channel Quantum dot solids with high electron and hole mobilities have been assembled from chemically synthesized PbSe and PbTe nanocrystals68,76 Figure 1010c shows small-angle X-ray scattering at grazing incidence (GISAXS) from a self-assembled lm of 8-nm PbSe nanocrystals The appearance of well-resolved re ections con rms both in-plane and vertical particle ordering in the PbSe nanocrystal assemblies Lead chalcogenide (PbS, PbSe, PbTe) nanocrystal solids offer smaller and Ec and larger values compared with II VI and III V nanocrystals These materials can be synthesized in the form of crystalline nanoparticles with very narrow size distributions (<5% std dev) (Fig 1010a,b), providing a higher density of electronic states available for the charge transport.

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The large Bohr radius of electrons and holes (eg, 23 nm for PbSe and 46 nm for PbTe) suggests that the electron and hole wavefunctions can effectively spill outside the volume of the nanocrystal, facilitating exchange interactions Bulk rocksalt PbSe and PbTe have very high static dielectric constants, 250 (PbSe) and 1000 (PbTe), cf 62 for CdSe This predicts an Ec < 4 meV for a 3D array of 8-nm PbSe nanocrystals, which is a small fraction of kT at room temperature68.

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