Preparation and characterisation of light emitting porous semiconductors

Semiconducting materials exhibit electrical conductivity in the region between that of metals and insulators. The electronic properties depend upon the particular element and the level of impurities contained within it. These materials are the basis of today's electronics industry with silicon being the most important element. It was believed until recently that efficient photoluminescence in the visible region was not possible from silicon due to its relatively small, indirect band-gap (1.12 eV). For this reason semiconductors with a larger, direct band-gap such as gallium arsenide have been used for optical devices. Photoluminescence from silicon has been observed in the infrared region but this was of little use to the opto-electronics industry. However, when silicon is in the form of small nano-structures, photoluminescence can be observed in the visible region from red to blue. This photoluminescence corresponds to a shift in the band gap to between 1.5 eV and 4.5 eV. This is in accordance with the predictions of quantum mechanics for structures of this scale. Nano-structures of silicon and of other semiconductors are relatively easy to produce. Electro-chemical etching is by far the most reliable method, resulting in uniform and reproducible structures. Anodic etching in a hydrofluoric acid based etch solution results in the silicon becoming porous to a depth of the order of microns. The lateral dimensions of these porous structures are in the range of a few nanometres resulting in an aspect ratio of the order of 1000:1. These materials studied in this work have been studied with the aid of EXAFS, scanning probe microscopy and Muon spectroscopy in order to determine the local structures. Measurements of the photoluminescence intensity have been taken at the synchrotron radiation facility, (Daresbury Laboratory). These results show that the observed photoluminescence is temperature dependent. The porous silicon samples studied for this work showed photoluminescence in the range yellow to red. The photoluminescence intensity was seen to decrease with an increase in temperature. Correspondingly the peak wavelength shifted (by between 12 and 40 nm) towards the blue end of the spectrum as the temperature was reduced from room temperature to 100 K. Scanning probe microscopy and scanning electron microscopy revealed the presence of structures within the porous matrix of the order of nanometres. This size of structure is consistent with that predicted by quantum mechanics for the shift in energy levels associated with quantum confinement. (author)