Electrical and Optical Doping of Silicon by Pulsed-Laser Melting

Over four decades ago, pulsed-laser melting, or pulsed-laser annealing as it was termed at that time, was the subject of intense study as a potential advance in silicon device processing. In particular, it was found that nanosecond laser melting of the near-surface of silicon and subsequent liquid phase epitaxy could not only very effectively remove lattice disorder following ion implantation, but could achieve dopant electrical activities exceeding equilibrium solubility limits. However, when it was realised that solid phase annealing at longer time scales could achieve similar results, interest in pulsed-laser melting waned for over two decades as a processing method for silicon devices. With the emergence of flat panel displays in the 1990s, pulsed-laser melting was found to offer an attractive solution for large area crystallisation of amorphous silicon and dopant activation. This method gave improved thin film transistors used in the panel backplane to define the pixelation of displays. For this application, ultra-rapid pulsed laser melting remains the crystallisation method of choice since the heating is confined to the silicon thin film and the underlying glass or plastic substrates are protected from thermal degradation. This article will be organised chronologically, but treatment naturally divides into the two main topics: (1) an electrical doping research focus up until around 2000, and (2) optical doping as the research focus after that time. In the first part of this article, the early pulsed-laser annealing studies for electrical doping of silicon are reviewed, followed by the more recent use of pulsed-lasers for flat panel display fabrication. In terms of the second topic of this review, optical doping of silicon for efficient infrared light detection, this process requires deep level impurities to be introduced into the silicon lattice at high concentrations to form an intermediate band within the silicon bandgap. The chalcogen elements and then transition metals were investigated from the early 2000s since they can provide the required deep levels in silicon. However, their low solid solubilities necessitated ultra-rapid pulsed-laser melting to achieve supersaturation in silicon many orders of magnitude beyond the equilibrium solid solubility. Although infrared light absorption has been demonstrated using this approach, significant challenges were encountered in attempting to achieve efficient optical doping in such cases, or hyperdoping as it has been termed. Issues that limit this approach include: lateral and surface impurity segregation during solidification from the melt, leading to defective filaments throughout the doped layer; and poor efficiency of collection of photo-induced carriers necessary for the fabrication of photodetectors. The history and current status of optical hyperdoping of silicon with deep level impurities is reviewed in the second part of this article.