Phosphorescence

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"Phosphorescent" redirects here. For the indie rock band, see Phosphorescent (band).
In common use, phosphorescence also refers to the emission of light by bioluminescent
plankton, and some other forms of chemoluminescence.

Phosphorescence

Phosphorescent powder under visible light, ultraviolet light, and total darkness.
Phosphorescence is a specific type of photoluminescence related to fluorescence. Unlike
fluorescence, a phosphorescent material does not immediately re-emit the radiation it
absorbs. The slower time scales of the re-emission are associated with "forbidden" energy
state transitions in quantum mechanics. As these transitions occur very slowly in certain
materials, absorbed radiation may be re-emitted at a lower intensity for up to several hours
after the original excitation.
Simple

In simple terms, phosphorescence is a process in which energy absorbed by a substance is

released relatively slowly in the form of light. This is in some cases the mechanism used for
"glow-in-the-dark" materials which are "charged" by exposure to light. Unlike the relatively
swift reactions in a common fluorescent tube, phosphorescent materials used for these
materials absorb the energy and "store" it for a longer time as the processes required to reemit the light occur less often.

Energy scheme used to explain the difference between fluorescence and phosphorescence

[edit] Quantum mechanical

After an electron absorbs a photon of high energy, it may undergo vibrational relaxations and
intersystem crossing to another spin state. Again the system relaxes vibrationally in the new spin
state and eventually emits light by phosphorescence.

Most photoluminescent events, in which a chemical substrate absorbs and then re-emits a
photon of light, are fast, on the order of 10 nanoseconds. Light is absorbed and emitted at
these fast time scales in cases where the energy of the photons involved matches the available
energy states and allowed transitions of the substrate. In the special case of phosphorescence,
the absorbed photon energy undergoes an unusual intersystem crossing into an energy state of
higher spin multiplicity (see term symbol), usually a triplet state. As a result, the energy can
become trapped in the triplet state with only classically "forbidden" transitions available to
return to the lower energy state. These transitions, although "forbidden", will still occur in
quantum mechanics but are kinetically unfavored and thus progress at significantly slower
time scales. Most phosphorescent compounds are still relatively fast emitters, with triplet
lifetimes on the order of milliseconds. However, some compounds have triplet lifetimes up to
minutes or even hours, allowing these substances to effectively store light energy in the form
of very slowly degrading excited electron states. If the phosphorescent quantum yield is high,

these substances will release significant amounts of light over long time scales, creating socalled "glow-in-the-dark" materials.
[edit] Equation

where S is a singlet and T a triplet whose subscripts denote states (0 is the ground state, and 1
the excited state). Transitions can also occur to higher energy levels, but the first excited state
is denoted for simplicity.

[edit] Chemiluminescence
Main article: Chemiluminescence

Some examples of "glow-in-the-dark" materials do not glow by phosphorescence. For

example, "glow sticks" glow due to a chemiluminescent process which is commonly
mistaken for phosphorescence. In chemiluminescence, an excited state is created via a
chemical reaction. The light emission tracks the kinetic progress of the underlying chemical
reaction. The excited state will then transfer to a "dye" molecule, also known as a sensitizer
or fluorophor, and subsequently fluoresce back to the ground state

[edit] Materials
Common pigments used in phosphorescent materials include zinc sulfide and strontium
aluminate. Use of zinc sulfide for safety related products dates back to the 1930s. However,
the development of strontium oxide aluminate, with a luminance approximately 10 times
greater than zinc sulfide, has relegated most zinc sulfide based products to the novelty
category. Strontium oxide aluminate based pigments are now used in exit signs, pathway
marking, and other safety related signage.[2]

Phosphorescent pigments - comparison ZnS vs. aluminate

left: Zinc sulfide, right: SrAl2O4

pigments in the dark

pigments in the dark after 4 min

Phosphorescent pigments red and blue

phosphorescent pigment red (Calcium sulfide)

phosphorescent pigment red in the dark

phosphorescent pigment blue (alkaline earth metal silicate )

phosphorescent pigment blue in the dark

This section requires expansion.

An extremely intense pulse of UV light in a flashtube produced this blue phosphorescence in

the fused silica envelope.
Commonly seen examples of phosphorescent materials are the glow-in-the-dark toys, paint,
and clock dials that glow for some time after being charged with a bright light such as in any
normal reading or room light. Typically the glowing then slowly fades out within minutes (or
up to a few hours) in a dark room.[1]
The study of phosphorescent materials led to the discovery of radioactivity in 1896.

Contents
[hide]

1 Explanations
o 1.1 Simple
o 1.2 Quantum mechanical
1.2.1 Equation
2 Chemiluminescence
3 Materials
4 See also
5 References
6 External links

Fluorescence is the emission of light by a substance that has absorbed light or other
electromagnetic radiation. It is a form of luminescence. In most cases, emitted light has a
longer wavelength, and therefore lower energy, than the absorbed radiation. However, when
the absorbed electromagnetic radiation is intense, it is possible for one electron to absorb two
photons; this two-photon absorption can lead to emission of radiation having a shorter
wavelength than the absorbed radiation. The emitted radiation may also be of the same
wavelength as the absorbed radiation, termed "resonance fluorescence".[1]

The most striking examples of fluorescence occur when the absorbed radiation is in the
ultraviolet region of the spectrum, and thus invisible to the human eye, and the emitted light
is in the visible region.
Fluorescence has many practical applications, including mineralogy, gemology, chemical
sensors (fluorescence spectroscopy), fluorescent labelling, dyes, biological detectors, and,
most commonly, fluorescent lamps.

History
An early observation of fluorescence was described by Nicols Monardes in 1565 in the
infusion of a certain type of wood (Lignum nephriticum).[2] The chemical compound
responsible for this fluorescence is matlanine, which is the oxidation product of one of the
flavonoids found in this wood.[3] In 1819 Edward D. Clarke and in 1822 Ren Juste Hay
described fluorescence in fluorites, Sir David Brewster described the phenomenon for
chlorophyll in 1833 and Sir John Herschel did the same for quinine in 1845.
In his 1852 paper on the "Refrangibility" (wavelength change) of light, George Gabriel
Stokes described the ability of fluorspar and uranium glass to change invisible light beyond
the violet end of the visible spectrum into blue light. He named this phenomenon
fluorescence.[4] He chose the name "to denote the general appearance of a solution of sulphate
of quinine and similar media".[5] The name was derived from the mineral fluorite (calcium
difluoride), some examples of which contain traces of divalent europium, which serves as the
fluorescent activator to emit blue light. In a key experiment he used a prism to isolate
ultraviolet radiation from sunlight and observed blue light emitted by an ethanol solution of
quinine exposed by it.

[edit] Physical Principles

[edit] Photochemistry

Fluorescence occurs when an orbital electron of a molecule, atom or nanostructure relaxes to

its ground state by emitting a photon of light after being excited to a higher quantum state by
some type of energy:
Excitation:
Fluorescence (emission):
here
is a generic term for photon energy with h = Planck's constant and = frequency of
light. (The specific frequencies of exciting and emitted light are dependent on the particular
system.)
State S0 is called the ground state of the fluorophore (fluorescent molecule) and S1 is its first
(electronically) excited state.
A molecule, S1, can relax by various competing pathways. It can undergo 'non-radiative
relaxation' in which the excitation energy is dissipated as heat (vibrations) to the solvent.

Excited organic molecules can also relax via conversion to a triplet state, which may
subsequently relax via phosphorescence or by a secondary non-radiative relaxation step.
Relaxation of an S1 state can also occur through interaction with a second molecule through
fluorescence quenching. Molecular oxygen (O2) is an extremely efficient quencher of
fluorescence just because of its unusual triplet ground state.
Molecules that are excited through light absorption or via a different process (e.g. as the
product of a reaction) can transfer energy to a second 'sensitized' molecule, which is
converted to its excited state and can then fluoresce. This process is used in lightsticks to
produce different colors.
[edit] Quantum yield

The fluorescence quantum yield gives the efficiency of the fluorescence process. It is defined
as the ratio of the number of photons emitted to the number of photons absorbed.[6][7]

The maximum fluorescence quantum yield is 1.0 (100%); every photon absorbed results in a
photon emitted. Compounds with quantum yields of 0.10 are still considered quite
fluorescent. Another way to define the quantum yield of fluorescence, is by the rate of
excited state decay:

where

is the rate of spontaneous emission of radiation and

is the sum of all rates of excited state decay. Other rates of excited state decay are caused by
mechanisms other than photon emission and are, therefore, often called "non-radiative rates",
which can include: dynamic collisional quenching, near-field dipole-dipole interaction (or
resonance energy transfer), internal conversion, and intersystem crossing. Thus, if the rate of
any pathway changes, both the excited state lifetime and the fluorescence quantum yield will
be affected.
Fluorescence quantum yields are measured by comparison to a standard. The quinine salt
quinine sulfate in a sulfuric acid solution is a common fluorescence standard.

[edit] Lifetime

Jablonski diagram. After an electron absorbs a high energy photon the system is excited
electronically and vibrationally. The system relaxes vibrationally, and eventually fluoresces at a
longer wavelength.

The fluorescence lifetime refers to the average time the molecule stays in its excited state
before emitting a photon. Fluorescence typically follows first-order kinetics:

where
is the concentration of excited state molecules at time ,
is the initial
concentration and is the decay rate or the inverse of the fluorescence lifetime. This is an
instance of exponential decay. Various radiative and non-radiative processes can de-populate
the excited state. In such case the total decay rate is the sum over all rates:

where
is the total decay rate,
the radiative decay rate and
the non-radiative
decay rate. It is similar to a first-order chemical reaction in which the first-order rate constant
is the sum of all of the rates (a parallel kinetic model). If the rate of spontaneous emission, or
any of the other rates are fast, the lifetime is short. For commonly used fluorescent
compounds, typical excited state decay times for photon emissions with energies from the
UV to near infrared are within the range of 0.5 to 20 nanoseconds. The fluorescence lifetime
is an important parameter for practical applications of fluorescence such as fluorescence
resonance energy transfer and Fluorescence-lifetime imaging microscopy.

[edit] Jablonski diagram

The Jablonski diagram describes most of the relaxation mechanisms for excited state
molecules.
[edit] Fluorescence anisotropy

Fluorophores are more likely to be excited by photons if the transition moment of the
fluorophore is parallel to the electric vector of the photon.[8] The polarization of the emitted
light will also depend on the transition moment. The transition moment is dependent on the
physical orientation of the fluorophore molecule. For fluorophores in solution this means that
the intensity and polarization of the emitted light is dependent on rotational diffusion.
Therefore, anisotropy measurements can be used to investigate how freely a fluorescent
molecule moves in a particular environment.
Fluorescence anisotropy can defined quantitatively as

where is the emitted intensity parallel to polarization of the excitation light and
emitted intensity perpendicular to the polarization of the excitation light.[9]

is the

[edit] Rules
There are several general rules that deal with fluorescence. Each of the following rules has
exceptions but they are useful guidelines for understanding fluorescence. (These rules do no
neccessarily apply to Two-photon absorption.)
[edit] Kasha-Vavilov rule

The KashaVavilov rule dictates that the quantum yield of luminescence is independent of
the wavelength of exciting radiation.[10] This occurs because excited molecules usually decay
to the lowest vibrational level of the excited state before fluorescence emission takes place.
The Kasha-Vavilov rule does not always apply and is violated severely in many simple
molecules. A somewhat more reliable statement, although still with exceptions, would be that
the fluorescence spectrum shows very little dependence on the wavelength of exciting
radiation.
[edit] Mirror image rule

For many fluorophores the absorption spectra is a mirror image of the emission spectra.[11]
This is known as the mirror image rule and is related to the FranckCondon principle which
states that electronic transitions are vertical, that is energy changes without distance changing
as can be represented with a vertical line in Jablonski diagram. This means the nucleus does
not move and the vibration levels of the excited state to resemble the vibration levels of the
ground state.

[edit] Stokes shift

In general, emitted fluorescent light has a longer wavelength and lower energy than the
absorbed light.[12] This phenomenon, known as Stokes shift, is due to energy loss between the
time a photon is absorbed and when it is emitted. The causes and magnitude of Stokes shift
can be complex and are dependent on the fluorophore and its environment. However, there
are some common causes. It is frequently due to non-radiative decay to the lowest vibrational
energy level of the excited state. Another factor is that the emission of fluorescence
frequently leaves a fluorophore in the highest vibrational level of the ground state.

[edit] Fluorescence in nature

There are many natural compounds that exhibit fluorescence, and they have a number of
applications. Some deep-sea animals, such as the greeneye, use fluorescence.
[edit] Gemology, mineralogy, and geology

Gemstones, minerals, may have a distinctive fluorescence or may fluoresce differently under
short-wave ultraviolet, long-wave ultraviolet, or X-rays.
Many types of calcite and amber will fluoresce under shortwave UV. Rubies, emeralds, and
the Hope Diamond exhibit red fluorescence under short-wave UV light; diamonds also emit
light under X ray radiation.
Fluorescence in minerals is caused by a wide range of activators. In some cases, the
concentration of the activator must be restricted to below a certain level, to prevent
quenching of the fluorescent emission. Furthermore, certain impurities such as iron or copper
need to be absent, to prevent quenching of possible fluorescence. Divalent manganese, in
concentrations of up to several percent, is responsible for the red or orange fluorescence of
calcite, the green fluorescence of willemite, the yellow fluorescence of esperite, and the
orange fluorescence of wollastonite and clinohedrite. Hexavalent uranium, in the form of the
uranyl cation, fluoresces at all concentrations in a yellow green, and is the cause of
fluorescence of minerals such as autunite or andersonite, and, at low concentration, is the
cause of the fluorescence of such materials as some samples of hyalite opal. Trivalent
chromium at low concentration is the source of the red fluorescence of ruby. Divalent
europium is the source of the blue fluorescence, when seen in the mineral fluorite. Trivalent
lanthanides such as terbium and dysprosium are the principal activators of the creamy yellow
fluorescence exhibited by the yttrofluorite variety of the mineral fluorite, and contribute to
the orange fluorescence of zircon. Powellite (calcium molybdate) and scheelite (calcium
tungstate) fluoresce intrinsically in yellow and blue, respectively. When present together in
solid solution, energy is transferred from the higher-energy tungsten to the lower-energy
molybdenum, such that fairly low levels of molybdenum are sufficient to cause a yellow
emission for scheelite, instead of blue. Low-iron sphalerite (zinc sulfide), fluoresces and
phosphoresces in a range of colors, influenced by the presence of various trace impurities.
Crude oil (petroleum) fluoresces in a range of colors, from dull-brown for heavy oils and tars
through to bright-yellowish and bluish-white for very light oils and condensates. This
phenomenon is used in oil exploration drilling to identify very small amounts of oil in drill
cuttings and core samples.

[edit] Organic liquids

Organic solutions such anthracene or stilbene, dissolved in benzene or toluene, fluoresce with
ultraviolet or gamma ray irradiation. The decay times of this fluorescence are of the order of
nanoseconds, since the duration of the light depends on the lifetime of the excited states of
the fluorescent material, in this case anthracene or stilbene.[citation needed]
[edit] Common materials that fluoresce

Vitamin B2 fluoresces yellow.

Tonic water fluoresces blue due to the presence of quinine.

[edit] Applications of fluorescence

[edit] Lighting
For more details on this topic, see Fluorescent lamp.

Fluorescent paint and plastic lit by UV tubes. Paintings by Beo Beyond

The common fluorescent lamp relies on fluorescence. Inside the glass tube is a partial
vacuum and a small amount of mercury. An electric discharge in the tube causes the mercury
atoms to emit ultraviolet light. The tube is lined with a coating of a fluorescent material,
called the phosphor, which absorbs the ultraviolet and re-emits visible light. Fluorescent
lighting is more energy-efficient than incandescent lighting elements. However, the uneven
spectrum of traditional fluorescent lamps may cause certain colors to appear different than
when illuminated by incandescent light or daylight. The mercury vapor emission spectrum is
dominated by a short-wave UV line at 254 nm (which provides most of the energy to the
phosphors), accompanied by visible light emission at 436 nm (blue), 546 nm (green) and
579 nm (yellow-orange). These three lines can be observed superimposed on the white
continuum using a hand spectroscope, for light emitted by the usual white fluorescent tubes.
These same visible lines, accompanied by the emission lines of trivalent europium and
trivalent terbium, and further accompanied by the emission continuum of divalent europium
in the blue region, comprise the more discontinuous light emission of the modern
trichromatic phosphor systems used in many compact fluorescent lamp and traditional lamps
where better color rendition is a goal.[13]
Fluorescent lights were first available to the public at the 1939 New York World's Fair.
Improvements since then have largely been better phosphors, longer life, and more consistent

internal discharge, and easier-to-use shapes (such as compact fluorescent lamps). Some highintensity discharge (HID) lamps couple their even-greater electrical efficiency with phosphor
enhancement for better color rendition.[citation needed]
White light-emitting diodes (LEDs) became available in the mid-1990s as LED lamps, in
which blue light emitted from the semiconductor strikes phosphors deposited on the tiny chip.
The combination of the blue light that continues through the phosphor and the green to red
fluorescence from the phosphors produces a net emission of white light.[citation needed]
Glow sticks sometimes utilize fluorescent materials to absorb light from the
chemiluminescent reaction and emit light of a different color.[13]
[edit] Analytical chemistry

Many analytical procedures involve the use of a fluorometer, usually with a single exciting
wavelength and single detection wavelength. Because of the sensitivity that the method
affords, fluorescent molecule concentrations as low as 1 part per trillion can be
measured.[citation needed]
Fluorescence in several wavelengths can be detected by an array detector, to detect
compounds from HPLC flow. Also, TLC plates can be visualized if the compounds or a
coloring reagent is fluorescent. Fluorescence is most effective when there is a larger ratio of
atoms at lower energy levels in a Boltzmann distribution. There is, then, a higher probability
of excitement and release of photons by lower-energy atoms, making analysis more efficient.
[edit] Spectroscopy
Main article: Fluorescence spectroscopy

Usually the setup of a Fluorescence assay involves a Light source, which may emit an array
different wavelengths of light. In general, a single wavelength is required for proper analysis,
so, in order to selectively filter the light, it is passed through an excitation monochromator,
and then that chosen wavelength is passed through the sample cell. After absorption and reemission of the energy, many wavelengths may emerge due to Stokes shift and various
electron transitions. To separate and analyze them, the fluorescent radiation is passed through
an Emission monochromator, and observed selectively by a detector.[14]
[edit] Biochemistry and medicine
Main article: Fluorescence in the life sciences

Endothelial cells under the microscope with three separate channels marking specific cellular
components

Fluorescence in the life sciences is used generally as a non-destructive way of tracking or

analysis of biological molecules by means of the fluorescent emission at a specific frequency
where there is no background from the excitation light, as relatively few cellular components
are naturally fluorescent (called intrinsic or autofluorescence). In fact, a protein or other
component can be "labelled" with an extrinsic fluorophore, a fluorescent dye that can be a
small molecule, protein, or quantum dot, finding a large use in many biological
applications.[15]
The quantification of a dye is done with a spectrofluorometer and finds additional
applications in:
[edit] Microscopy

When scanning the fluorescent intensity across a plane one has fluorescence microscopy of
tissues, cells, or subcellular structures, which is accomplished by labeling an antibody with a
fluorophore and allowing the antibody to find its target antigen within the sample. Labelling
multiple antibodies with different fluorophores allows visualization of multiple targets
within a single image (multiple channels). DNA microarrays are a variant of this.
Immunology: An antibody is first prepared by having a fluorescent chemical group attached,
and the sites (e.g., on a microscopic specimen) where the antibody has bound can be seen,
and even quantified, by the fluorescence.
FLIM (Fluorescence Lifetime Imaging Microscopy) can be used to detect certain biomolecular interactions that manifest themselves by influencing fluorescence lifetimes.
Cell and molecular biology: detection of colocalization using fluorescence-labelled antibodies
for selective detection of the antigens of interest using specialized software, such as
CoLocalizer Pro.

[edit] Other techniques

FRET Fluorescence resonance energy transfer is used to study protein interactions, detect
specific nucleic acid sequences and used as biosensors, while fluorescence lifetime (FLIM)
can give an additional layer of information.
Biotechnology: biosensors using fluorescence are being studied as possible Fluorescent
glucose biosensors.
Automated sequencing of DNA by the chain termination method; each of four different
chain terminating bases has its own specific fluorescent tag. As the labelled DNA molecules
are separated, the fluorescent label is excited by a UV source, and the identity of the base
terminating the molecule is identified by the wavelength of the emitted light.
FACS (fluorescence-activated cell sorting). One of several important cell sorting techniques
used in the separation of different cell lines (especially those isolated from animal tissues).
DNA detection: the compound ethidium bromide, in aqueous solution, has very little
fluorescence, as it is quenched by water. Ethidium bromide's fluorescence is greatly
enhanced after it binds to DNA, so this compound is very useful in visualising the location of
DNA fragments in agarose gel electrophoresis. Intercalated ethidium is in a hydrophobic
environment when it is between the base pairs of the DNA, protected from quenching by

water which is excluded from the local environment of the intercalated ethidium. Ethidium
bromide may be carcinogenic an arguably safer alternative is the dye SYBR Green.
[edit] Forensics

Fingerprints can be visualized with fluorescent compounds such as ninhydrin. Blood and
other substances are sometimes detected by fluorescent reagents, like fluorescein. Fibers, and
other materials that may be encountered in forensics or with a relationship to various
collectibles, are sometimes fluorescent.

[edit] See also

Absorption-re-emission atomic line filters use the phenomenon of fluorescence to filter light
extremely effectively.
Black light
Blacklight paint
Evos microscope
Fluorescence correlation spectroscopy
Fluorescence in plants
Fluorescence spectroscopy
Fluorescent lamp
Fluorescent multilayer card
Fluorescent Multilayer Disc
Fluorometer
High-visibility clothing
Laser-induced fluorescence
List of light sources
Mssbauer effect, resonant fluorescence of gamma rays
Organic light-emitting diodes can be fluorescent
Phosphorescence
Phosphor thermometry, the use of phosphorescence to measure temperature.
Spectroscopy
Two-photon absorption
X-ray fluorescence

[edit]