Photoluminescence (abbreviated as PL) is a process in which a substance absorbs photons (electromagnetic radiation) and then re-radiates photons. Quantum mechanically, this can be described as an excitation to a higher energy state and then a return to a lower energy state accompanied by the emission of a photon. This is one of many forms of luminescence (light emission) and is distinguished by photoexcitation (excitation by photons), hence the prefix photo-. The period between absorption and emission is typically extremely short, in the order of 10 nanoseconds. Under special circumstances, however, this period can be extended into minutes or hours.

Ultimately, available chemical energy states and allowed transitions between states (and therefore wavelengths of light preferentially absorbed and emitted) are determined by the rules of quantum mechanics. A basic understanding of the principles involved can be gained by studying the electron configurations and molecular orbitals of simple atoms and molecules. More complicated molecules and advanced subtleties are treated in the field of computational chemistry.

Forms of photoluminescence

The simplest photoluminescent processes are resonant radiations, in which a photon of a particular wavelength is absorbed and an equivalent photon is immediately emitted. This process involves no significant internal energy transitions of the chemical substrate between absorption and emission and is extremely fast, of the order of 10 nanoseconds.

More interesting processes occur when the chemical substrate undergoes internal energy transitions before re-emitting the energy from the absorption event. The most familiar such effect is fluorescence, which is also typically a fast process, but in which some of the original energy is dissipated so that the emitted light photons are of lower energy than those absorbed. The generated photon in this case is said to be red shifted, referring to the loss of energy as Jablonski diagram shows.

Photoluminescence is an important technique for measuring the purity and crystalline quality of semiconductors such as GaAs and InP. Several variations of photoluminescence exist, including photoluminescence excitation (PLE).

An even more specialized form of photoluminescence is phosphorescence, in which the energy from absorbed photons undergoes intersystem crossing into a state of higher spin multiplicity (see term symbol), usually a triplet state. Once the energy is trapped in the triplet state, transition back to the lower singlet energy states is quantum mechanically forbidden, meaning that it happens much more slowly than other transitions. The result is a slow process of radiative transition back to the singlet state, sometimes lasting minutes or hours. This is the basis for "glow in the dark" substances.

References

Further reading

Donald A. McQuarrie, John D. Simon Physical Chemistry, a molecular approach. University Science Books.