Fluorescence and Phosphorescence

Fluorescence and Phosphorescence

The ability of a material to emit various wavelengths of light is similarly related to its atomic energy levels. This figure shows a scorpion illuminated by a UV lamp, sometimes called a black light. Some rocks also glow in black light, the particular colors being a function of the rock’s mineral composition. Black lights are also used to make certain posters glow.

Objects glow in the visible spectrum when illuminated by an ultraviolet (black) light. Emissions are characteristic of the mineral involved, since they are related to its energy levels. In the case of scorpions, proteins near the surface of their skin give off the characteristic blue glow. This is a colorful example of fluorescence in which excitation is induced by UV radiation while de-excitation occurs in the form of visible light. (credit: Ken Bosma, Flickr)

In the fluorescence process, an atom is excited to a level several steps above its ground state by the absorption of a relatively high-energy UV photon. This is called atomic excitation. Once it is excited, the atom can de-excite in several ways, one of which is to re-emit a photon of the same energy as excited it, a single step back to the ground state. This is called atomic de-excitation. All other paths of de-excitation involve smaller steps, in which lower-energy (longer wavelength) photons are emitted. Some of these may be in the visible range, such as for the scorpion in this figure. Fluorescence is defined to be any process in which an atom or molecule, excited by a photon of a given energy, and de-excites by emission of a lower-energy photon.

Fluorescence can be induced by many types of energy input. Fluorescent paint, dyes, and even soap residues in clothes make colors seem brighter in sunlight by converting some UV into visible light. X rays can induce fluorescence, as is done in x-ray fluoroscopy to make brighter visible images. Electric discharges can induce fluorescence, as in so-called neon lights and in gas-discharge tubes that produce atomic and molecular spectra. Common fluorescent lights use an electric discharge in mercury vapor to cause atomic emissions from mercury atoms. The inside of a fluorescent light is coated with a fluorescent material that emits visible light over a broad spectrum of wavelengths. By choosing an appropriate coating, fluorescent lights can be made more like sunlight or like the reddish glow of candlelight, depending on needs. Fluorescent lights are more efficient in converting electrical energy into visible light than incandescent filaments (about four times as efficient), the blackbody radiation of which is primarily in the infrared due to temperature limitations.

This atom is excited to one of its higher levels by absorbing a UV photon. It can de-excite in a single step, re-emitting a photon of the same energy, or in several steps. The process is called fluorescence if the atom de-excites in smaller steps, emitting energy different from that which excited it. Fluorescence can be induced by a variety of energy inputs, such as UV, x-rays, and electrical discharge.

The spectacular Waitomo caves on North Island in New Zealand provide a natural habitat for glow-worms. The glow-worms hang up to 70 silk threads of about 30 or 40 cm each to trap prey that fly towards them in the dark. The fluorescence process is very efficient, with nearly 100% of the energy input turning into light. (In comparison, fluorescent lights are about 20% efficient.)

Fluorescence has many uses in biology and medicine. It is commonly used to label and follow a molecule within a cell. Such tagging allows one to study the structure of DNA and proteins. Fluorescent dyes and antibodies are usually used to tag the molecules, which are then illuminated with UV light and their emission of visible light is observed. Since the fluorescence of each element is characteristic, identification of elements within a sample can be done this way.

This figure shows a commonly used fluorescent dye called fluorescein. Below that, this figure reveals the diffusion of a fluorescent dye in water by observing it under UV light.

Fluorescein, shown here in powder form, is used to dye laboratory samples. (credit: Benjah-bmm27, Wikimedia Commons)

Here, fluorescent powder is added to a beaker of water. The mixture gives off a bright glow under ultraviolet light. (credit: Bricksnite, Wikimedia Commons)

Microscopic image of chicken cells using nano-crystals of a fluorescent dye. Cell nuclei exhibit blue fluorescence while neurofilaments exhibit green. (credit: Weerapong Prasongchean, Wikimedia Commons)

Once excited, an atom or molecule will usually spontaneously de-excite quickly. (The electrons raised to higher levels are attracted to lower ones by the positive charge of the nucleus.) Spontaneous de-excitation has a very short mean lifetime of typically about \({\text{10}}^{-8}\phantom{\rule{0.25em}{0ex}}\text{s}\). However, some levels have significantly longer lifetimes, ranging up to milliseconds to minutes or even hours. These energy levels are inhibited and are slow in de-exciting because their quantum numbers differ greatly from those of available lower levels.

Although these level lifetimes are short in human terms, they are many orders of magnitude longer than is typical and, thus, are said to be metastable, meaning relatively stable. Phosphorescence is the de-excitation of a metastable state. Glow-in-the-dark materials, such as luminous dials on some watches and clocks and on children’s toys and pajamas, are made of phosphorescent substances. Visible light excites the atoms or molecules to metastable states that decay slowly, releasing the stored excitation energy partially as visible light. In some ceramics, atomic excitation energy can be frozen in after the ceramic has cooled from its firing. It is very slowly released, but the ceramic can be induced to phosphoresce by heating—a process called “thermoluminescence.” Since the release is slow, thermoluminescence can be used to date antiquities. The less light emitted, the older the ceramic. (See this figure.)

Atoms frozen in an excited state when this Chinese ceramic figure was fired can be stimulated to de-excite and emit EM radiation by heating a sample of the ceramic—a process called thermoluminescence. Since the states slowly de-excite over centuries, the amount of thermoluminescence decreases with age, making it possible to use this effect to date and authenticate antiquities. This figure dates from the 11^th century. (credit: Vassil, Wikimedia Commons)