Electronic transport in mixed-phase hydrogenated amorphous/nanocrystalline silicon thin films

The opto-electronic properties of amorphous/nanocrystalline hydrogenated silicon (a/nc-Si:H) mixed-phase thin films are investigated. Small crystalline silicon particles (3-5 nm diameter) synthesized in a flow-through reactor are injected into a separate capacitively-coupled plasma (CCP) chamber where mixed-phase hydrogenated amorphous silicon is grown by Plasma Enhanced Chemical Vapor Deposition (PECVD) deposition techniques. This dual-chamber co-deposition system enables the variation of crystallite concentration incorporated into a series of a-Si:H films deposited simultaneously. The structural, optical and electronic properties of these mixed-phase materials are studied as a function of the silicon nanocrystal concentration. That is, we compare a sequence of films deposited in a single run, where the location of the substrate in the CCP chamber determines the density of embedded nanocrystals. Raman spectroscopy is used to determine the volume fraction of nanocrystals in the mixed phase thin films. At a moderate concentration of silicon crystallites, the dark conductivity and photoconductivity are consistently found to be up to several orders of magnitude higher than in mixed phase films with either low or heavy nanocrystalline inclusions. These results are interpreted in terms of a model whereby for low nanocrystal concentrations conduction is influenced by the disorder introduced into the a-Si:H film by the inclusions, while at high nanocrystal densities electronic transport is described by a heterojunction quantum dot model. The thermopower of the undoped a/nc-Si:H has a lower Seebeck coefficient, and similar temperature dependence, to that observed for undoped a-Si:H. In contrast, the addition of nanoparticles in doped a/nc-Si:H thin films leads to a negative Seebeck coefficient (consistent with n-type doping) with a positive temperature dependence, that is, the Seebeck coefficient becomes larger at higher temperatures. The temperature dependence of the thermopower of the doped a/nc-Si:H is similar to that observed in unhydrogenated a-Si grown by sputtering or following high-temperature annealing of a-Si:H, suggesting that charge transport may occur via hopping in these materials.