Optical properties of group 12-16 (ii-vi) semiconductor nanoparticles  (Page 4/5)

Uv-visible absorbance

Due to the presence of discrete energy levels in a QD, there is a widening of the energy gap between the highest occupied electronic states and the lowest unoccupied states as compared to the bulk material. As a consequence, the optical properties of the semiconductor nanoparticles also become size dependent.

The minimum energy required to create an exciton is the defined by the band gap of the material, i.e., the energy required to excite an electron from the highest level of valence energy states to the lowest level of the conduction energy states. For a quantum dot, the bandgap varies with the size of the particle. From [link] and [link] , it can be inferred that the band gap becomes higher as the particle becomes smaller. This means that for a smaller particle, the energy required for an electron to get excited is higher. The relation between energy and wavelength is given by [link] , where h is the Planck’s constant, c is the speed of light, λ is the wavelength of light. Therefore, from [link] to cross a bandgap of greater energy, shorter wavelengths of light are absorbed, i.e., a blue shift is seen.

For Group 12-16 semiconductors, the bandgap energy falls in the UV-visible range. That is ultraviolet light or visible light can be used to excite an electron from the ground valence states to the excited conduction states. In a bulk semiconductor the band gap is fixed, and the energy states are continuous. This results in a rather uniform absorption spectrum ( [link] a).

In the case of Group 12-16 quantum dots, since the bandgap can be changed with the size, these materials can absorb over a range of wavelengths. The peaks seen in the absorption spectrum ( [link] b) correspond to the optical transitions between the electron and hole levels. The minimum energy and thus the maximum wavelength peak corresponds to the first exciton peak or the energy for an electron to get excited from the highest valence state to the lowest conduction state. The quantum dot will not absorb wavelengths of energy longer than this wavelength. This is known as the absorption onset.

Fluorescence

Fluorescence is the emission of electromagnetic radiation in the form of light by a material that has absorbed a photon. When a semiconductor quantum dot (QD) absorbs a photon/energy equal to or greater than its band gap, the electrons in the QD’s get excited to the conduction state. This excited state is however not stable. The electron can relax back to its ground state by either emitting a photon or lose energy via heat losses. These processes can be divided into two categories – radiative decay and non-radiative decay. Radiative decay is the loss of energy through the emission of a photon or radiation. Non-radiative decay involves the loss of heat through lattice vibrations and this usually occurs when the energy difference between the levels is small. Non-radiative decay occurs much faster than radiative decay.