To fully deploy the potential of semiconductor nanocrystal films as low-cost electronic materials, a better understanding of the amount of dopants required to make their conductivity metallic is needed. In bulk semiconductors, the critical concentration of electrons at the metal-insulator transition is described by the Mott criterion. Here, we theoretically derive the critical concentration nc for films of heavily doped nanocrystals devoid of ligands at their surface and in direct contact with each other. In the accompanying experiments, we investigate the conduction mechanism in films of phosphorus-doped, ligand-free silicon nanocrystals. At the largest electron concentration achieved in our samples, which is half the predicted nc, we find that the localization length of hopping electrons is close to three times the nanocrystals diameter, indicating that the film approaches the metal-insulator transition.Semiconductor nanocrystals (NCs) have shown great potential in optoelectronics applications such as solar cells [1], light emitting diodes [2], and field-effect transistors [3,4] by virtue of their size-tunable optical and electrical properties [5] and low-cost solution-based processing techniques [6,7]. These applications require conducting NC films and the introduction of extra carriers through doping can enhance the electrical conduction. Several strategies for NC doping have been developed. Remote doping, the use of suitable ligands as donors in the vicinity of NC surface, increased the conductivity of PbSe NC films by 12 orders of magnitude [8]. Electrochemical doping, which tunes the carrier concentration accurately and reversibly, resulted in conducting NC films [9,10]. Lately, stoichiometric control has emerged as a strategy to dope lead chalcogenide NCs [11]. Finally, electronic impurity doping of NCs, originally impeded by synthetic challenges [12], was recently achieved in InAs [13] and CdSe [14] NCs.While many experimental studies have been directed towards increasing the conductivity of NC films, there is still no clear consensus on the fundamental question: what is the condition for the metal-insulator transition (MIT) in NC films [15][16][17]? In a bulk semiconductor, the critical electron concentration n M for the MIT depends on the Bohr radius a B according to the well-known Mott criterion [18] n M a 3 B 0.02, where a B = ε 2 /m * e 2 is the effective Bohr radius (in Gaussian units), ε is the dielectric constant of the semiconductor, and m * is the effective electron mass. It is obvious that a dense film of undoped semiconductor NCs is an insulator, while a film of touching metallic NCs with the same geometry is a conductor. Therefore, the MIT has to occur in semiconductor NC films at some criti-FIG. 1. The origin of the metal-to-insulator transition in semiconductor nanocrystal films. The figure shows the cross section of two nanocrystals in contact through facets with radius ρ. The blue spherical cloud represents an electron wave packet which moves through the contact. Such a compact wave pac...